U.S. patent application number 13/731920 was filed with the patent office on 2013-07-18 for uv-curable adhesive silicone composition, uv-curable adhesive silicone composition sheet, optical semiconductor apparatus and method for manufacturing the same.
This patent application is currently assigned to SHIN-ETSU CHEMICAL CO., LTD.. The applicant listed for this patent is SHIN-ETSU CHEMICAL CO., LTD.. Invention is credited to Tsutomu KASHIWAGI, Toshio SHIOBARA.
Application Number | 20130183776 13/731920 |
Document ID | / |
Family ID | 47603199 |
Filed Date | 2013-07-18 |
United States Patent
Application |
20130183776 |
Kind Code |
A1 |
KASHIWAGI; Tsutomu ; et
al. |
July 18, 2013 |
UV-CURABLE ADHESIVE SILICONE COMPOSITION, UV-CURABLE ADHESIVE
SILICONE COMPOSITION SHEET, OPTICAL SEMICONDUCTOR APPARATUS AND
METHOD FOR MANUFACTURING THE SAME
Abstract
A UV-curable adhesive silicone composition includes: (A) an
organopolysiloxane having a resin structure consisting of
R.sup.1SiO.sub.3/2, R.sup.2.sub.2SiO.sub.2/2, and
R.sup.3.sub.aR.sup.4.sub.bSiO.sub.(4-a-b)/2 units, wherein R.sup.4
represents a vinyl group or an allyl group, wherein 5 to 300
R.sup.2.sub.2SiO.sub.2/2 units are continuously repeated, (B) an
organohydrogenpolysiloxane having a resin structure consisting of
R.sup.1SiO.sub.3/2, R.sup.2.sub.2SiO.sub.2/2, and
R.sup.3.sub.cH.sub.dSiO.sub.(4-c-d)/2 units, wherein 5 to 300
R.sup.2.sub.2SiO.sub.2/2 units are continuously repeated, and (C) a
photoactive catalyst, wherein the UV-curable adhesive silicone
composition is in a plastic solid state or a semi-solid state in an
uncured state at room temperature. Thereby, there can be provided a
UV-curable adhesive silicone composition that is in a plastic solid
state or a semi-solid state in an uncured state at room temperature
and therefore easy to handle, can uniformly disperse a phosphor and
cover a surface of an LED chip, and can readily form a cured layer
only on a necessary portion.
Inventors: |
KASHIWAGI; Tsutomu; (Annaka,
JP) ; SHIOBARA; Toshio; (Annaka, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SHIN-ETSU CHEMICAL CO., LTD.; |
Tokyo |
|
JP |
|
|
Assignee: |
SHIN-ETSU CHEMICAL CO.,
LTD.
Tokyo
JP
|
Family ID: |
47603199 |
Appl. No.: |
13/731920 |
Filed: |
December 31, 2012 |
Current U.S.
Class: |
438/26 ;
522/66 |
Current CPC
Class: |
C08G 77/12 20130101;
G03F 7/0757 20130101; H01L 2224/48091 20130101; C08G 77/20
20130101; C09J 183/04 20130101; H01L 33/56 20130101; C08G 77/80
20130101; C08G 77/70 20130101; H01L 23/296 20130101; H01L
2224/45144 20130101; H01L 2224/48091 20130101; C08L 83/04 20130101;
G03F 7/0758 20130101; H01L 2224/73265 20130101; H01L 2924/00
20130101; H01L 2924/00014 20130101; C08L 2205/02 20130101; G03F
7/0751 20130101; G03F 7/40 20130101; H01L 2224/45144 20130101 |
Class at
Publication: |
438/26 ;
522/66 |
International
Class: |
C09J 183/04 20060101
C09J183/04; H01L 33/56 20060101 H01L033/56 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 18, 2012 |
JP |
2012-7890 |
Claims
1. A UV-curable adhesive silicone composition comprising: (A) an
organopolysiloxane having a resin structure consisting of
R.sup.1SiO.sub.3/2, R.sup.2.sub.2SiO.sub.2/2, and
R3.sub.aR4.sub.bSiO.sub.(4-a-b)/2 units, wherein, R.sup.1, R.sup.2
and R.sup.3 each independently represent any one of a hydroxyl
group, a methyl group, an ethyl group, a propyl group, a cyclohexyl
group, and a phenyl group, R.sup.4 represents a vinyl group or an
allyl group, a represents 0, 1 or 2, b represents 1, 2 or 3, and
a+b represents 2 or 3, wherein at least a part of
R.sup.2.sub.2SiO.sub.2/2 units is continuously repeated and the
number of repetitions thereof is 5 to 300, (B) an
organohydrogenpolysiloxane having a resin structure consisting of
R.sup.1SiO.sub.3/2, R.sup.2.sub.2SiO.sub.2/2, and
R.sup.3.sub.cH.sub.dSiO.sub.(4-c-d)/2 units, wherein R.sup.1,
R.sup.2 and R.sup.3 each independently represent the same as that
described above, c represents 0, 1 or 2, d represents 1 or 2, and
c+d represents 2 or 3, wherein at least a part of
R.sup.2.sub.2SiO.sub.2/2 units is continuously repeated and the
number of repetitions thereof is 5 to 300, and (C) a photoactive
catalyst, wherein the UV-curable adhesive silicone composition is
in a plastic solid state or a semi-solid state in an uncured state
at room temperature.
2. The UV-curable adhesive silicone composition according to claim
1, wherein the UV-curable adhesive silicone composition further
contains (D) a phosphor.
3. The UV-curable adhesive silicone composition according to claim
2, wherein 0.1 to 100 parts by mass of the phosphor of the (D)
component are contained with respect to 100 parts by mass of a sum
total of the (A) to (C) components.
4. The UV-curable adhesive silicone composition according to claim
2, wherein a particle size of the (D) phosphor is 10 nm or
more.
5. The UV-curable adhesive silicone composition according to claim
3, wherein a particle size of the (D) phosphor is 10 nm or
more.
6. The UV-curable adhesive silicone composition according to claim
1, wherein the total number of moles of hydrogen atoms directly
bonded to silicon atoms in the (B) component with respect to the
total number of moles of vinyl groups and allyl groups in the (A)
component is an amount to be 0.1 to 4.0 by mole ratio.
7. The UV-curable adhesive silicone composition according to claim
2, wherein the total number of moles of hydrogen atoms directly
bonded to silicon atoms in the (B) component with respect to the
total number of moles of vinyl groups and allyl groups in the (A)
component is an amount to be 0.1 to 4.0 by mole ratio.
8. The UV-curable adhesive silicone composition according to claim
3, wherein the total number of moles of hydrogen atoms directly
bonded to silicon atoms in the (B) component with respect to the
total number of moles of vinyl groups and allyl groups in the (A)
component is an amount to be 0.1 to 4.0 by mole ratio.
9. The UV-curable adhesive silicone composition according to claim
4, wherein the total number of moles of hydrogen atoms directly
bonded to silicon atoms in the (B) component with respect to the
total number of moles of vinyl groups and allyl groups in the (A)
component is an amount to be 0.1 to 4.0 by mole ratio.
10. The UV-curable adhesive silicone composition according to claim
5, wherein the total number of moles of hydrogen atoms directly
bonded to silicon atoms in the (B) component with respect to the
total number of moles of vinyl groups and allyl groups in the (A)
component is an amount to be 0.1 to 4.0 by mole ratio.
11. The UV-curable adhesive silicone composition according to claim
1, wherein at least one of the R.sup.1, R.sup.2 and R.sup.3 is a
hydroxyl group.
12. The UV-curable adhesive silicone composition according to claim
2, wherein at least one of the R.sup.1, R.sup.2 and R.sup.3 is a
hydroxyl group.
13. A UV-curable adhesive silicone composition sheet obtained by
forming the UV-curable adhesive silicone composition according to
claim 1 into sheet-form.
14. A UV-curable adhesive silicone composition sheet obtained by
forming the UV-curable adhesive silicone composition according to
claim 2 into sheet-form.
15. An optical semiconductor apparatus manufactured by using the
UV-curable adhesive silicone composition sheet according to claim
13.
16. An optical semiconductor apparatus manufactured by using the
UV-curable adhesive silicone composition sheet according to claim
14.
17. A method of manufacturing an optical semiconductor apparatus,
comprising the steps of: disposing the UV-curable adhesive silicone
composition sheet according to claim 13 on a surface of an optical
semiconductor device; irradiating light; and heating after
that.
18. A method of manufacturing an optical semiconductor apparatus,
comprising the steps of: disposing the UV-curable adhesive silicone
composition sheet according to claim 14 on a surface of an optical
semiconductor device; irradiating light; and heating after that.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a UV-curable adhesive
silicone composition, a UV-curable adhesive silicone composition
sheet, an optical semiconductor apparatus, and a method for
manufacturing the same.
[0003] 2. Description of the Related Art
[0004] At the present time, since a silicone resin is excellent in
the light resistance, it gathers an attention as a material for
covering for sealing and protecting a light-emitting diode (LED)
device (see Patent Literature 1). Further, in a field of
light-emitting diodes, it is well known to use a phosphor as a
wavelength converter (see Patent Literature 2). As a film in which
a phosphor is dispersed, a thermosetting silicone resin is put into
practical use (see Patent Literature 3). However, since a
hydrosilylation reaction is used to cure, in many cases, a
platinum-based catalyst is added in advance in a thermosetting
silicone resin composition. As a result, from immediately after
compounding, the reaction proceeds; accordingly, also a reaction
control agent is added to secure the pot life. However, as a result
thereof, a curing speed of the composition becomes slow and the
composition flows during heat-curing to cause a problem of
deformation of a shape thereof.
[0005] Further, in Patent Literature 4, a photocurable
organopolysiloxane composition containing
(methylcyclopentadienyl)trimethyl platinum as a curing catalyst is
disclosed. The (methylcyclopentadienyl)trimethyl platinum is
activated only when light is irradiated thereon; accordingly, under
a non-irradiated state, the viscosity of the organopolysiloxane
composition does not increase and the pot life is excellent. The
Patent Literature 4 discloses a method where, upon irradiation of a
light in an irradiation wavelength region of 200 nm to 400 nm, the
(methylcyclopentadienyl)trimethyl platinum catalyst is activated to
cure the organopolysiloxane composition.
[0006] However, according to a method of the Patent Literature 4,
since a property before curing has fluidity, there is a problem
that a resin composition flows before the organosiloxane
composition is completely cured, and a cured material having a
target shape can not be obtained.
[0007] Further, in some cases, it is necessary to cover only an
optical semiconductor device (an LED chip, for example) or to form
a bonding pad; accordingly, a film that can be patterned by
lithography, which is not the conventional thermal curing type, is
in demand. Still further, in LEDs, a resin layer that covers a LED
chip is demanded to have also high thermal resistance and UV-ray
resistance. Further, it is convenient when such a resin layer can
be formed according to an existing manufacturing apparatus.
[0008] Further, generally in white LEDs, a method where by covering
an LED chip with a silicone resin or an epoxy resin, in which a
phosphor is dispersed, the phosphor is dispersed in the vicinity of
the chip to convert a blue light into a pseudo-white light is
adopted. However, when the phosphor is irregularly dispersed or
unevenly concentrated, color deviation tends to occur. Accordingly,
in order to obtain a uniform white light, it is necessary to
uniformly disperse the phosphor in a covering resin layer. For this
purpose, a method has been studied, in which, by applying a screen
printing method or a sedimentation method, the phosphor is
sedimented to disperse in the vicinity of a lower portion of the
covering resin layer. However, there was a problem that a
manufacturing step is made complicated and the degree of obtained
stability is insufficient. Accordingly, an easy technology that
allows to uniformly disperse a phosphor on a chip surface is in
demand.
CITATION LIST
Patent Literature
[0009] [Patent Document 1] Japanese Patent Laid-Open Publication
No. 2004-339482
[0010] [Patent Document 2] Japanese Translation of PCT
International Application No. 2005-524737
[0011] [Patent Document 3] Japanese Patent Laid-Open Publication
No. 2009-235368
[0012] [Patent Document 4] Japanese Patent Laid-Open Publication
No. 2010-47646
SUMMARY OF THE INVENTION
[0013] The present invention was carried out in view of the above
situation, and it is an object of the invention to provide a
UV-curable adhesive silicone composition that can be cured while
maintaining an initial shape without allowing a resin composition
to flow during heat-curing, and, further, a UV-curable adhesive
silicone composition that can form an adhesive silicone composition
sheet that (1) is in a plastic solid state or a semi-solid state in
an uncured state at room temperature and can be readily handled,
(2) when containing a phosphor therein, can uniformly disperse the
phosphor and has a stable dispersion state thereof with time, and
(3) can readily cover a surface of a semiconductor device
(including an optical semiconductor device such as an LED device
and so on) and, by curing only a necessary portion with a UV light
source and a mask, can readily form a resin cured layer.
[0014] In order to solve the problem, according to the invention, a
UV-curable adhesive silicone composition that includes [0015] (A)
an organopolysiloxane having a resin structure consisting of
R.sup.1SiO.sub.3/2, R.sup.2.sub.2SiO.sub.2/2, and
R.sup.3.sub.aR.sup.4.sub.bSiO.sub.(4-a-b)/2 units, wherein R.sup.1,
R.sup.2 and R.sup.3 each independently represent any one of a
hydroxyl group, a methyl group, an ethyl group, a propyl group, a
cyclohexyl group, and a phenyl group, R.sup.4 represents a vinyl
group or an allyl group, a represents 0, 1 or 2, b represents 1, 2
or 3, and a+b represents 2 or 3, wherein at least a part of
R.sup.2.sub.2SiO.sub.2/2 units is continuously repeated and the
number of repetitions thereof is 5 to 300, [0016] (B) an
organohydrogenpolysiloxane having a resin structure consisting of
R.sup.1SiO.sub.3/2, R.sup.2.sub.2SiO.sub.2/2, and
R.sup.3.sub.cH.sub.dSiO.sub.(4-c-d)/2 units, wherein R.sup.1,
R.sup.2 and R.sup.3 each independently represent the same as that
in the above, c represents 0, 1 or 2, d represents 1 or 2, and c+d
represents 2 or 3, wherein at least a part of
R.sup.2.sub.2SiO.sub.2/2 units is continuously repeated and the
number of repetitions thereof is 5 to 300, and [0017] (C) a
photoactive catalyst, wherein the UV-curable adhesive silicone
composition is in a plastic solid state or a semi-solid state in an
uncured state at room temperature is provided.
[0018] Such the UV-curable adhesive silicone composition becomes a
UV-curable adhesive silicone composition that can be cured while
maintaining an initial shape without allowing the resin composition
to flow during heat-curing. Further, according to the UV-curable
adhesive silicone composition, a UV-curable adhesive silicone
composition sheet that; is in a plastic solid state or a semi-solid
state in an uncured state (that is, under non-heat treatment) at
room temperature and can be readily handled; and, can readily cover
a surface of an optical semiconductor device, and by curing only a
necessary portion with a UV-light source and a mask, can readily
form a resin cured layer can be formed.
[0019] In the present invention, the "semi-solid" means a state
that does not have the fluidity while having the plasticity and
shows a liquid or solid property depending on an external stress
such as temperature, stress, and strain.
[0020] Further, the "room temperature" shows an environmental
temperature in a usual state, usually in the range of 15 to
30.degree. C., and typically 25.degree. C.
[0021] Further, in this case, the UV-curable adhesive silicone
composition preferably further contains (D) a phosphor.
[0022] Even when the UV-curable adhesive silicone composition
contains the (D) phosphor like this, a resin cured layer in which
the phosphor is uniformly dispersed and the dispersion state
thereof is stable with time can be obtained.
[0023] Further, in this case, the UV-curable adhesive silicone
composition preferably contains 0.1 to 100 parts by mass of the
phosphor of the (D) component with respect to 100 parts by mass of
a sum total of the (A) to (C) components.
[0024] When a compounding amount of the phosphor of the (D)
component is set like this, a resin cured layer obtained from the
UV-curable adhesive silicone composition can more surely absorb a
light from the optical semiconductor device and can convert into a
light of different wavelength.
[0025] , in this case, a particle size of the (D) phosphor is
preferable to be 10 nm or more.
[0026] Like this, a particle size of the phosphor of the (D)
component is preferable to be 10 nm or more, more preferable to be
10 nm to 10 .mu.m, and particularly preferable to be 10 nm to about
1 .mu.m.
[0027] Further, in this case, the UV-curable adhesive silicone
composition preferably contains an amount of 0.1 to 4.0 by mole
ratio of the total number of moles of hydrogen atoms directly
bonded to silicon atoms in the (B) component with respect to the
total number of moles of vinyl groups and allyl groups in the (A)
component.
[0028] When a compounding amount of the (B) component is set like
this, a hydrosilylation reaction between the (A) component and the
(B) component is excellently proceeded.
[0029] Further, in this case, at least one of the R.sup.1, R.sup.2
and R.sup.3 can be a hydroxyl group.
[0030] Thus, in the (A) component and/or the (B) component of the
composition of the invention, a silanol group can be contained.
[0031] Further, according to the invention, a UV-curable adhesive
silicone composition sheet obtained by forming the UV-curable
adhesive silicone composition into sheet-form is provided.
[0032] Thus, a UV-curable adhesive silicone composition sheet
obtained by forming the UV-curable adhesive silicone composition of
the present invention into sheet-form is easy to handle and
excellent in the workability, and can be readily adhered by
stacking on a surface of an optical semiconductor device such as an
LED chip. Further, the UV-curable adhesive silicone composition
sheet is in a plastic solid state or a semi-solid state in an
uncured state; accordingly, charged phosphor does not cause
separation and precipitation during storage. Accordingly, a resin
cured layer where the phosphor is uniformly dispersed therein can
be stably formed.
[0033] Further, the present invention provides an optical
semiconductor apparatus manufactured by using the UV-curable
adhesive silicone composition sheet.
[0034] According to the optical semiconductor apparatus
manufactured by using the UV-curable adhesive silicone composition
sheet of the present invention, a resin cured layer that covers an
optical semiconductor device has high heat resistance and light
transmittance. Further, an optical semiconductor apparatus having
an optical semiconductor device that is covered with the resin
cured layer in which the phosphor is uniformly dispersed is
obtained.
[0035] Further, the present invention provides a method of
manufacturing an optical semiconductor apparatus, which includes a
step of disposing the UV-curable adhesive silicone composition
sheet on a surface of an optical semiconductor device, a step of
irradiating light, and a step of heating after that.
[0036] When the UV-curable adhesive silicone composition sheet of
the present invention is disposed on a surface of an optical
semiconductor device such as an LED chip or the like, the LED chip
can be readily covered. Further, when lithography is applied with a
UV-light source and a mask on the sheet, only a necessary portion
can be cured in gel, and, after that, by dissolving and developing
an unnecessary uncured portion with a solvent, a resin cured layer
can be formed only on a necessary portion.
[0037] A UV-curable adhesive silicone composition of the present
invention can be cured while maintaining an initial shape without
allowing the resin composition to flow during heating and curing.
Further, since a UV-curable adhesive silicone composition sheet
obtained by forming the composition in sheet is in a plastic solid
state or a semi-solid state in an uncured state, it can be readily
handled and is excellent in the workability, and can be readily
stacked and adhered to a surface of a semiconductor device even
with a mounting machine such as a usual die bonding machine.
Further, a charged phosphor does not separate and precipitate
during storage. Then, when the composition sheet is cured, a resin
cured layer in which the phosphor is uniformly dispersed can be
efficiently and stably formed with a uniform layer thickness. That
is, the mass productivity is excellent. Further, in the resulted
phosphor-containing resin cured layer, the phosphor is uniformly
dispersed; accordingly, color deviation is difficult to occur, that
is, the color rendering properties are excellent. Still further,
the resulted cured material becomes a cured material (resin cured
layer) that is, while being a hard resin, excellent in the
flexibility and less in surface tackiness.
BRIEF DESCRIPTION OF THE DRAWING
[0038] FIG. 1 is a schematic diagram illustrating an LED apparatus
having a flip-chip structure, which is prepared for measuring
chromaticity in an example.
DESCRIPTION OF THE EMBODIMENTS
[0039] Hereinafter, the present invention will be described in more
detail.
[0040] As was described above, a composition for covering an
optical semiconductor device had a problem that the composition
flows before completion of curing to result in being unable to
obtain a cured material having a target shape and a problem that
the dispersion of the phosphor in the resin layer becomes irregular
or is deviated.
[0041] In this connection, a UV-curable adhesive silicone
composition that can be cured while maintaining an initial shape
without causing the resin composition to flow during heat-curing,
and that can form an adhesive silicone composition sheet that is
easy to handle, in which the phosphor is uniformly dispersed and a
dispersion state thereof is stable with time is in demand.
[0042] The inventors, after studying hard to achieve the object,
came to complete the present invention. That is, the present
invention is a DV-curable adhesive silicone composition
characterized by including: [0043] (A) an organopolysiloxane having
a resin structure consisting of R.sup.1SiO.sub.3/2,
R.sup.2.sub.2SiO.sub.2/2, and
R.sup.3.sub.aR.sup.4.sub.bSiO.sub.(4-a-b)/2 units, wherein R.sup.1,
R.sup.2 and R.sup.3 each independently represent any one of a
hydroxyl group, a methyl group, an ethyl group, a propyl group, a
cyclohexyl group, and a phenyl group, R.sup.4 represents a vinyl
group or an allyl group, a represents 0, 1 or 2, b represents 1, 2
or 3, and a+b represents 2 or 3, wherein at least a part of
R.sup.2.sub.2SiO.sub.2/2 units is continuously repeated and the
number of repetitions thereof is 5 to 300, [0044] (B) an
organohydrogenpolysiloxane having a resin structure consisting of
R.sup.1SiO.sub.3/2, R.sup.2.sub.2SiO.sub.2/2, and
R.sup.3.sub.cH.sub.dSiO.sub.(4-c-d)/2 units, wherein R.sup.1,
R.sup.2 and R.sup.3 each independently represent the same as that
in the above, c represents 0, 1 or 2, d represents 1 or 2, and c+d
represents 2 or 3, wherein at least a part of
R.sup.2.sub.2SiO.sub.2/2 units is continuously repeated and the
number of repetitions thereof is 5 to 300, and [0045] (C) a
photoactive catalyst, wherein the UV-curable adhesive silicone
composition is in a plastic solid state or a semi-solid state in an
uncured state at room temperature.
[0046] Hereinafter, the invention will be described in more detail.
In the following description, Me, Et, Ph and Vi respectively
represent a methyl group, an ethyl group, a phenyl group and a
vinyl group.
UV-Curable Adhesive Silicone Composition
[0047] --(A) Organopolysiloxane having Resin Structure--
[0048] An organopolysiloxane having a resin structure (that is,
three-dimensional network structure), which is an important (A)
component of a UV-curable adhesive silicone composition of the
present invention, is an organopolysiloxane that has a resin
structure that consists of R.sup.1SiO.sub.3/2,
R.sup.2.sub.2SiO.sub.2/2, and
R.sup.3.sub.aR.sup.4.sub.bSiO.sub.(4-a-b)/2 units, (wherein
R.sup.1, R.sup.2 and R.sup.3 each independently represent any one
of a hydroxyl group, a methyl group, an ethyl group, a propyl
group, a cyclohexyl group, and a phenyl group, R.sup.4 represents a
vinyl group or an allyl group, a represents 0, 1 or 2, b represents
1, 2 or 3, and a+b represents 2 or 3), and the organopolysiloxane
partially includes a structure where at least a part of
R.sup.2.sub.2SiO.sub.2/2 units is continuously repeated and the
number of repetitions thereof is 5 to 300, preferably 10 to 300,
more preferably 15 to 200, and still preferably 20 to 100.
[0049] A structure where at least a part of
R.sup.2.sub.2SiO.sub.2/2 units is continuously repeated and the
number of repetitions thereof is 5 to 300, which is described
above, means a linear diorganopolysiloxane chain architecture
represented by a formula (1),
##STR00001##
wherein R.sup.2 represents the same as that in the above, and m
represents an integer of 5 to 300.
[0050] It is preferable that at least a part of an entirety of
R.sup.2.sub.2SiO.sub.2/2 units present in organopolysiloxane of an
(A) component, preferably 50% by mole or more (50 to 100% by mole),
particularly 80% by mole or more (80 to 100% by mole) preferably
forms a chain architecture represented by such a formula (1) in a
molecule.
[0051] In a molecule of the (A) component, R.sup.2.sub.2SiO.sub.2/2
units work to linearly stretch a polymer molecule, and
R.sup.1SiO.sub.3/2 units make a polymer molecule to branch or form
a three-dimensional network structure. R.sup.4 (vinyl group or
allyl group) in R.sup.3.sub.aR.sup.4.sub.bSiO.sub.(4-a-b)/2 units
plays, by undergoing a hydrosilylation addition reaction with a
hydrogen atom bonded to a silicon atom (that is, SiH group) of
R.sup.3.sub.cH.sub.dSiO.sub.(4-c-d)/2 units that the (B) component
described below has, a role of curing the composition of the
present invention.
[0052] A mole ratio of indispensable three kinds of siloxane units
that constitute the (A) component, that is, a mole ratio of
R.sup.1SiO.sub.3/2 units:R.sup.2.sub.2SiO.sub.2/2
units:R.sup.3.sub.aR.sup.4.sub.bSiO.sub.(4-a-b)/2 units is
preferable to be 90 to 24:75 to 9:50 to 1, and particularly
preferable to be 70 to 28:70 to 20:10 to 2 (sum total thereof is
100) from the viewpoint of the characteristics of the resulted
cured material.
[0053] When an weight average molecular weight of the (A) component
in terms of polystyrene according to gel permeation chromatography
(GPC) with tetrahydrofuran (THF) as an eluent is in the range of
3,000 to 1,000,000, in particular, 10,000 to 100,000, the polymer
is more surely in a plastic solid state or a semi-solid state and
suitable from the viewpoint of workability and curability.
[0054] The organopolysiloxane having such the resin structure can
be synthesized in such a manner that compounds that is raw
materials of the respective units are combined so that the three
kinds of siloxane units may be a predetermined mole ratio in a
generated polymer, and, for example, under the presence of acid, a
cohydrolysis condensation is conducted.
[0055] Herein, as a raw material of the R.sup.1SiO.sub.3/2 unit,
chlorosilanes such as MeSiCl.sub.3, EtSiCl.sub.3, PhSiCl.sub.3,
propyltrichlorosilane and cyclohexyl trichlorosilane, and
alkoxysilanes such as methoxysilanes corresponding to the
respective chlorosilanes can be exemplified.
[0056] As the raw materials of the R.sup.2.sub.2SiO.sub.2/2 units,
ClMe.sub.2SiO(Me.sub.2SiO).sub.nSiMe.sub.2Cl,
ClMe.sub.2SiO(Me.sub.2SiO).sub.m(PhMeSiO).sub.nSiMe.sub.2Cl,
ClMe.sub.2SiO(Me.sub.2SiO).sub.m(Ph.sub.2SiO).sub.nSiMe.sub.2Cl,
HOMe.sub.2SiO(Me.sub.2SiO).sub.nSiMe.sub.2OH,
HOMe.sub.2SiO(Me.sub.2SiO).sub.m(PhMeSiO).sub.11SiMe.sub.2OH,
HOMe.sub.2SiO(Me.sub.2SiO).sub.m(Ph.sub.2SiO).sub.nSiMe.sub.2OH,
MeOMe.sub.2SiO(Me.sub.2SiO).sub.nSiMe.sub.2OMe,
MeOMe.sub.2SiO(Me.sub.2SiO).sub.m(PhMeSiO).sub.nSiMe.sub.2OMe, and
MeOMe.sub.2SiO(Me.sub.2SiO).sub.m(Ph.sub.2SiO).sub.nSiMe.sub.2OMe
(herein, m represents an integer (average value) from 5 to 150, and
n represents an integer (average value) from 5 to 300)) can be
exemplified.
[0057] Further, R.sup.3.sub.aR.sup.4.sub.bSiO.sub.(4-a-b)/2 units
indicate one kind of siloxane unit selected from
R.sup.3R.sup.4SiO.sub.2/2, R.sup.3.sub.2R.sup.4SiO.sub.1/2,
R.sup.4.sub.2SiO.sub.2/2 and R.sup.3R.sup.4.sub.2SiO.sub.1/2 units
or a combination of two or more kinds of the siloxane units
selected therefrom. As the raw materials thereof, chlorosilanes
such as Me.sub.2ViSiCl, MeViSiCl.sub.2, Ph.sub.2ViSiCl, and
PhViSiCl.sub.2, and alkoxysilanes such as methoxysilanes
corresponding to each of these chlorosilanes can be
exemplified.
[0058] In the present invention, when the organopolysiloxane of the
(A) component is manufactured according to a cohydrolysis and
condensation of the raw compounds described above, in some cases,
R.sup.1SiO.sub.3/2 units, R.sup.2.sub.2SiO.sub.2/2 units, and/or
R.sup.3.sub.aR.sup.4.sub.bSiO.sub.(4-a-b)/2 units may contain a
siloxane unit having a silanol group. That is, there is a case
where a siloxane unit where at least one of R.sup.1, R.sup.2 and
R.sup.3 is a hydroxyl group is contained. The organopolysiloxane of
the (A) component may contain such the silanol group-containing
siloxane unit, with respect to an entire siloxane units, usually by
10% by mole or less (0 to 10% by mole), preferably by 5% by mole or
less (0 to 5% by mole). Examples of the silanol group-containing
siloxane units include R.sup.1(HO)SiO.sub.2/2,
R.sup.1(HO).sub.2SiO.sub.1/2, R.sup.2.sub.2(HO)SiO.sub.1/2,
R.sup.3R.sup.4(HO)SiO.sub.1/2, and R.sup.4.sub.2(HO)SiO.sub.1/2
units, wherein R.sup.1 to R.sup.4 are the same as that described
above.
--(B) Organohydrogenpolysiloxane having Resin Structure--
[0059] An organohydrogenpolysiloxane having a resin structure (that
is, three-dimensional network structure), which is an important (B)
component of the UV-curable adhesive silicone composition of the
present invention is an organohydrogenpolysiloxane that has a resin
structure that consists of R.sup.1SiO.sub.3/2,
R.sup.2.sub.2SiO.sub.2/2, and R.sup.3.sub.cH.sub.dSiO.sub.(4-c-d)/2
units (Here, R.sup.1, R.sup.2 and R.sup.3 are the same as that
described above, c represents 0, 1 or 2, d represents 1 or 2, and
c+d represents 2 or 3, desirably among
R.sup.3.sub.cH.sub.dSiO.sub.(4-c-d)/2 units, c represents 2 and d
represents 1), the organohydrogenpolysiloxane partially contains a
linear siloxane structure where at least a part of
R.sup.2.sub.2SiO.sub.2/2 units is continuously repeated and the
number of repetitions is 5 to 300, preferably 10 to 300, more
preferably 15 to 200, and still preferably 20 to 100.
[0060] The structure where at least a part of
R.sup.2.sub.2SiO.sub.2/2 units is continuously repeated and the
number of repetitions thereof is 5 to 300 means that at least a
part of R.sup.2.sub.2SiO.sub.2/2 units present in the (B)
component, preferably 50% by mole or more (50 to 100% by mole)
thereof, particularly 80% by mole or more (80 to 100% by mole)
thereof forms a linear diorganopolysiloxane chain architecture
represented by the formula (1) in the molecule of the (B)
component.
[0061] Also in a molecule of the (B) component,
R.sup.2.sub.2SiO.sub.2/2 units work to linearly stretch a polymer
molecule, and R.sup.1SiO.sub.3/2 units make a polymer molecule to
branch or form a three-dimensional network structure. A hydrogen
atom bonded to silicon in R.sup.3.sub.cH.sub.dSiO.sub.(4-c-d)/2
units plays, by undergoing a hydrosilylation addition reaction with
an alkenyl group that the (A) component has, a role of curing a
composition of the present invention.
[0062] A mole ratio of indispensable three kinds of siloxane units
that constitute the (B) component, that is, a mole ratio of
R.sup.1SiO.sub.3/2 units:R.sup.2.sub.2SiO.sub.2/2
units:R.sup.3.sub.cH.sub.dSiO.sub.(4-c-d)/2 units is preferable to
be 90 to 24:75 to 9:50 to 1, and particularly preferable to be 70
to 28:70 to 20:10 to 2 (sum total thereof is 100) from the
viewpoint of the characteristics of the resulted cured
material.
[0063] When a weight average molecular weight of the (B) component
in terms of polystyrene according to the GPC with tetrahydrofuran
(THF) as an eluent is in the range of 3,000 to 1,000,000, in
particular, 10,000 to 100,000, the polymer is suitable from the
viewpoint of workability and characteristics of the cured
material.
[0064] The organohydrogenpolysiloxane having such the resin
structure can be synthesized in such a manner that compounds that
is raw materials of the respective units are combined so that the
three kinds of siloxane units may be a predetermined mole ratio in
a generated polymer, and, a cohydrolysis is conducted.
[0065] Herein, as the raw materials of the R.sup.1SiO.sub.3/2 unit,
MeSiCl.sub.3, EtSiCl.sub.3, PhSiCl.sub.3, propyltrichlorosilane,
cyclohexyl trichlorosilane, and alkoxysilanes such as
methoxysilanes corresponding to the respective chlorosilanes can be
cited.
[0066] As the raw materials of the R.sup.2.sub.2SiO.sub.2/2 units,
ClMe.sub.2SiO(Me.sub.2SiO).sub.nSiMe.sub.2Cl,
ClMe.sub.2SiO(Me.sub.2SiO).sub.m(PhMeSiO).sub.nSiMe.sub.2Cl,
ClMe.sub.2SiO(Me.sub.2SiO).sub.m(Ph.sub.2SiO).sub.nSiMe.sub.2Cl,
HOMe.sub.2SiO(Me.sub.2SiO).sub.nSiMe.sub.2OH,
HOMe.sub.2SiO(Me.sub.2SiO).sub.m(PhMeSiO).sub.nSiMe.sub.2OH,
HOMe.sub.2SiO(Me.sub.2SiO).sub.m(Ph.sub.2SiO).sub.nSiMe.sub.2OH,
MeOMe.sub.2SiO(Me.sub.2SiO).sub.nSiMe.sub.2OMe,
MeOMe.sub.2SiO(Me.sub.2SiO).sub.m(PhMeSiO).sub.nSiMe.sub.2OMe, and
MeOMe.sub.2SiO(Me.sub.2SiO).sub.m(Ph.sub.2SiO).sub.mSiMe.sub.2OMe
(herein, m represents an integer (average value) of 5 to 150, and n
represents an integer (average value) of 5 to 300)) can be
exemplified.
[0067] Further, R.sup.3.sub.cH.sub.dSiO.sub.(4-c-d)/2 units
indicates one kind of siloxane unit selected from
R.sup.3HSiO.sub.2/2, R.sup.3.sub.2HSiO.sub.1/2, H.sub.2SiO.sub.2/2
and R.sup.3H.sub.2SiO.sub.1/2 units or an optional combination of
two or more kinds of siloxane units selected therefrom. As the raw
materials thereof, chlorosilanes such as Me.sub.2HSiCl,
MeHSiCl.sub.2, Ph.sub.2HSiCl, and PhHSiCl.sub.2, and alkoxysilanes
such as methoxysilanes corresponding to each of the chlorosilanes
can be exemplified.
[0068] In the present invention, when the
organohydrogenpolysiloxane of the (B) component is prepared
according to a cohydrolysis and condensation of the raw compounds,
in some cases, R.sup.1SiO.sub.3/2, R.sup.2.sub.2SiO.sub.2/2, and
R.sup.3.sub.cH.sub.dSiO.sub.(4-c-d)/2 units may contain a siloxane
unit having a silanol group. That is, in some cases, there is a
case where a siloxane unit where at least one of R.sup.1, R.sup.2
and R.sup.3 is a hydroxyl group is contained. The
organohydrogenpolysiloxane of the (B) component may contain such
the silanol group-containing siloxane unit, usually, with respect
to an entire siloxane units, by an amount of 10% by mole or less (0
to 10% by mole), preferably 5% by mole or less (0 to 5% by mole).
Examples of the silanol group-containing siloxane units include
R.sup.1(HO)SiO.sub.2/2, R.sup.1(HO).sub.2SiO.sub.1/2,
R.sup.2.sub.2(HO)SiO.sub.1/2, R.sup.3H(HO)SiO.sub.1/2, and
H.sub.2(HO)SiO.sub.1/2 units, wherein R.sup.1 to R.sup.3 are the
same as that described above.
[0069] A compounding amount of the organohydrogenpolysiloxane of
the (B) component is, in terms of a mole ratio of hydrogen atoms
bonded to silicon atoms (SiH groups) in the (B) component with
respect to a total amount of vinyl groups and ally groups in the
(A) component, preferably an amount to be 0.1 to 4.0, particularly
preferably an amount to be 0.5 to 3.0, and still more preferably an
amount to be 0.8 to 2.0. When the compounding amount is 0.1 or
more, a curing reaction preferably proceeds to be able to obtain a
silicone cured material, and when the compounding amount is 4.0 or
less, unreacted (residual) SiH groups in the cured material are
contained less and there is no fear of change with time of physical
properties of the cured material.
--(C) Photoactive Catalyst--
[0070] In hitherto known thermosetting silicone resin compositions,
in many cases, a platinum-based catalyst that is not photoactive is
added in advance (Patent Literature 3, for example). The present
invention is characterized by using a photoactive catalyst as a
catalyst. The (C) component is not restricted to particular one as
long as it is a catalyst having a photoactive property,
particularly a photoactive platinum group metal catalyst or
nickel-based catalyst can be cited. Examples of the platinum group
metal catalysts include a platinum-based catalyst, a
palladium-based catalyst and a rhodium-based catalyst. Among these,
the platinum-based catalyst is preferred. As the platinum-based
catalysts, .beta.-diketonate platinum complex catalysts such as
trimethyl(acetylacetonate)platinum complexes,
trimethyl(3,5-heptanedionate)platinum complexes,
trimethyl(methylacetoacetate)platinum complexes,
bis(2,4-pentanedionato)platinum complexes,
bis(2,4-hexanedionato)platinum complexes,
bis(2,4-heptanedionato)platinum complexes,
bis(3,5-heptanedionato)platinum complexes,
bis(1-phenyl-1,3-butanedionato)platinum complexes and
bis(1,3-diphenyl-1,3-propanedionato)platinum complexes can be
exemplified. Further, (methylcyclopentadienyl)trimethyl platinum
can be used. Examples of the nickel-based catalysts include
bis(2,4-pentanedionato)nickel complexes. These catalysts may be
used singularly or in a combination of two or more kinds thereof.
In particular, bis(2,4-pentanedionato)platinum complexes, whose
trivial name is bis(acetylacetonato) platinum(II), is preferably
used in the curing method of the present invention.
[0071] A compounding amount of the (C) component may be an
effective amount for curing, and, usually, is used, with respect to
a total amount of the (A) component and (B) component, in terms of
mass as platinum group metal, for example, in the range of 0.1 to
1000 ppm, particularly preferably 0.5 to 500 ppm.
[0072] According to a UV-curable adhesive silicone composition
containing the (A) to (C) components, the resin composition does
not flow during heat-curing and can be cured with an initial shape
maintained. Further, from the composition, an adhesive silicone
composition sheet that is in a plastic solid state or semi-solid
state in an uncured state at room temperature and can be readily
handled can be formed. Further, the adhesive silicone composition
sheet can be readily adhered to a surface of a semiconductor device
(including an optical semiconductor device such as an. LED device),
and, by curing only a necessary portion with a UV-light source and
a mask, a resin cured layer can be readily formed only on a
necessary portion.
[0073] In the UV-curable adhesive silicone composition of the
present invention, in addition to the above-described (A) to (C)
components, as required, various kinds of additives that are
heretofore-known can be compounded.
--(D) Phosphor--
[0074] When the UV-curable adhesive silicone composition of the
present invention is used to form a resin layer that coats an LED
device, the composition preferably contains, in addition to the
above-described (A) to (C) components, (D) a phosphor for
converting a wavelength. The UV-curable adhesive silicone
composition of the present invention, even in the case where (D)
the phosphor is contained like this, can obtain a resin cured layer
where the phosphor is uniformly dispersed and a state of dispersion
is stable with time.
[0075] The phosphor of the (D) component may be any of heretofore
known phosphors and a compounding amount thereof is usually set in
the range of 0.1 to 100 parts by mass with respect to 100 parts by
mass of a total amount of the (A) to (C). The phosphor of the (D)
component that has, as a range of a particle size in the particle
size distribution measurement according to a laser light
diffraction method using a Cirrus laser measurement apparatus,
etc., a particle size of, usually, 10 nm or more, preferably 10 nm
to 10 .mu.m, more preferably about 10 nm to 1 .mu.m is used.
[0076] A phosphor may be, for example, a material that absorbs a
light from a semiconductor light-emitting diode that has a
nitride-based semiconductor as a light-emitting layer and converts
to a light having a different wavelength. At least one or more
selected from nitride-based phosphors and oxynitride-based
phosphors mainly activated by a lanthanoid element such as Eu or
Ce; alkali earth halogen apatite phosphors, alkali earth metal
halogen borate phosphors, alkali earth metal aluminate phosphors,
alkali earth silicate phosphors, alkali earth sulfide phosphors,
alkali earth thiogallate phosphors, alkali earth silicon nitride
phosphors, and germinate phosphors mainly activated by a lanthanoid
element such as Eu or a transition metal element such as Mn; or
rare earth aluminate phosphors, rare earth silicate phosphors
mainly activated by a lanthanoid element such as Ce; or organic and
organo complex phosphors, Ca--Al--Si--O--N-based oxynitride glass
phosphors mainly activated by a lanthanoid element such as Eu is
preferred. As specific examples thereof, the following phosphors
can be used without limiting thereto.
[0077] As the nitride-based phosphors mainly activated by a
lanthanoid element such as Eu, Ce, M.sub.2Si.sub.5N.sub.8: Eu (M is
at least one kind selected from Sr, Ca, Ba, Mg and Zn.) can be
cited. Further, in addition to M.sub.2Si.sub.5N.sub.8: Eu,
MSi.sub.7N.sub.10: Eu, M.sub.1.8Si.sub.5O.sub.0.2N.sub.8: Eu, and
M.sub.0.9Si.sub.7O.sub.0.1N.sub.10: Eu (M is at least one kind
selected from Sr, Ca, Ba, Mg and Zn.) can be cited.
[0078] As the oxynitride-based phosphors mainly activated by a
lanthanoid element such as Eu, Ce include MSi.sub.2O.sub.2N.sub.2:
Eu (M is at least one kind selected from Sr, Ca, Ba, Mg and Zn.)
can be cited.
[0079] As the alkali earth halogen apatite phosphors mainly
activated by a lanthanoid element such as Eu and/or a transition
metal element such as Mn, M.sub.5(PO.sub.4).sub.3X: R (M is at
least one kind selected from Sr, Ca, Ba, Mg and Zn. X is at least
one kind selected from F, Cl, Br and I. R is at least one kind of
Eu, Mn, and Eu and Mn.) can be cited.
[0080] As the alkali earth metal halogen borate phosphors,
M.sub.2B.sub.5O.sub.9X: R (M is at least one kind selected from Sr,
Ca, Ba, Mg and Zn. X is at least one kind selected from F, Cl, Br
and I. R is least one kind of Eu, Mn, and Eu and Mn.) can be
cited.
[0081] As the alkali earth metal aluminate phosphors,
SrAl.sub.2O.sub.4: R, Sr.sub.4Al.sub.14O.sub.25: R,
CaAl.sub.2O.sub.4: R, BaMg.sub.2Al.sub.16O.sub.27: R,
BaMg.sub.2Al.sub.16O.sub.12: R, and BaMgAl.sub.10O.sub.17: R (R is
at least any one kind of Eu, Mn, and Eu and Mn.) can be cited.
[0082] As the alkali earth metal sulfide phosphors,
La.sub.2O.sub.2S: Eu, Y.sub.2O.sub.2S: Eu, and Gd.sub.2O.sub.2S: Eu
can be cited.
[0083] As the rare earth aluminate phosphors mainly activated by a
lanthanoid element such as Ce, YAG series phosphors represented by
a compositional formula such as Y.sub.3Al.sub.5O.sub.12: Ce,
(Y.sub.0.8Gd.sub.0.2).sub.3Al.sub.5O.sub.12: Ce,
Y.sub.3(Al.sub.0.8Ga.sub.0.2).sub.5O.sub.12: Ce and
(Y,Gd).sub.3(Al, Ga).sub.5O.sub.12 can be cited. Further,
Tb.sub.3Al.sub.5O.sub.12: Ce and Lu.sub.3Al.sub.5O.sub.12: Ce, in
which Y is partially or entirely substituted with Tb or Lu, etc.
can be cited.
[0084] As other phosphors, ZnS: Eu, Zn.sub.2GeO.sub.4: Mn, and
MGa.sub.2S.sub.4: Eu (M is at least one kind selected from Sr, Ca,
Ba, Mg and Zn. X is at least one kind selected from F, Cl, Br and
I.) can be cited.
[0085] The above phosphors may contain, as required, in place of
Eu, or in addition to Eu, one or more kind selected from Tb, Cu,
Ag, Au, Cr, Nd, Dy, Co, Ni and Ti.
[0086] The Ca--Al--Si--O--N series oxynitride glass phosphor
includes, as a matrix, an oxynitride glass that contains, by mole
%, 20 to 50% by mole of CaCO.sub.3 in terms of CaO, 0 to 30% by
mole of Al.sub.2O.sub.3, 25 to 60% by mole of SiO, 5 to 50% by mole
of AlN, and 0.1 to 20% by mole of rare earth oxide or transition
metal oxide, the sum total of 5 components being 100% by mole. In
the phosphor of which matrix is oxynitride glass, a content of
nitrogen is preferable to be 15% by weight or less, and, in
addition to a rare earth oxide ion, another rare earth element ion
that becomes a sensitizer is preferably contained as a co-activator
as a rare earth oxide in the content in the range of 0.1 to 10% by
mole in a phosphorescent glass.
[0087] Further, also phosphors other than the above phosphors,
which have the same performance and effects as that mentioned above
can be used.
Inorganic Filler:
[0088] Examples of the inorganic fillers include: reinforcing
inorganic fillers such as fumed silica and fumed titanium dioxide;
and nonreinforcing inorganic fillers such as calcium carbonate,
calcium silicate, titanium dioxide, ferric oxide, carbon black, and
zinc oxide. These inorganic fillers can be appropriately compounded
in total in the range of 600 parts by mass or less (0 to 600 parts
by weight) with respect to a sum total of 100 parts by mass of the
(A) component and (B) component.
Adhesive Auxiliary:
[0089] Further, in the composition of the present invention, in
order to further impart the adhesiveness, an adhesive auxiliary may
be added, as required. As the adhesive auxiliary, linear or cyclic
organosiloxane oligomer having 4 to 50, preferably about 4 to 20
silicon atoms, which contains in one molecule at least two kinds,
preferably two kinds or three kinds of functional groups selected
from a hydrogen atom bonded to a silicon atom (SiH group), an
alkenyl group bonded to a silicon atom (Si--CH.dbd.CH.sub.2 group,
for example), an alkoxysilyl group (trimethoxysilyl group, for
example), and an epoxy group (glycidoxypropyl group,
3,4-epoxycyclohexylethyl group, for example), and an
organooxysilyl-modified isocyanurate compound represented by the
following formula (2) and/or a hydrolytic condensate thereof
(organosiloxane-modified isocyanurate compound) can be cited.
##STR00002##
[0090] Wherein R.sup.19 represents an organic group represented by
the following formula (3),
##STR00003##
wherein R.sup.20 represents a hydrogen atom or a mono-valent
hydrocarbon group having 1 to 6 carbon atoms, s represents an
integer of 1 to 6, in particular, 1 to 4.) or a mono-valent
hydrocarbon group containing an aliphatic unsaturated bond, and at
least one of R.sup.19 is an organic group of the formula (3).
[0091] As the monovalent hydrocarbon groups that contains an
aliphatic unsaturated bond of R.sup.19 in the formula (2), alkenyl
groups having 2 to 8, particularly 2 to 6 carbon atoms, such as a
vinyl group, an allyl group, an isopropenyl group, a butenyl group,
an isobutenyl group, a pentenyl group and a hexenyl group and
cycloalkenyl groups having 6 to 8 carbon atoms such as a
cyclohexenyl group can be cited. Further, as the monovalent
hydrocarbon groups of R.sup.20 in the formula (3), monovalent
hydrocarbon groups having 1 to 8, particularly 1 to 6 carbon atoms
such as alkyl groups such as a methyl group, an ethyl group, a
propyl group, an isopropyl group, a butyl group, an isobutyl group,
a tert-butyl group, a pentyl group, a hexyl group and a cyclohexyl
group; alkenyl groups and cycloalkenyl groups exemplified of the
R.sup.19; and aryl groups such as a phenyl group can be cited, and
alkyl groups are preferably cited.
[0092] Further, as the adhesive auxiliaries, compounds represented
by the following formulas can be exemplified.
##STR00004##
[0093] (In the formula, g and h each represent a positive integer
in the range of 0 to 50, and g+h satisfies 2 to 50, preferably 4 to
20.)
##STR00005##
[0094] Among the organosilicon compounds, as compounds that can
impart particularly excellent adhesiveness to the resulted cured
material, organosilicon compounds having, in one molecule, an
alkoxy group bonded to a silicon atom, and an alkenyl group or a
hydrogen atom bonded to a silicon atom (SiH group) can be
cited.
[0095] A compounding amount of the adhesive auxiliary is, with
respect to 100 parts by mass of the (A) component, usually 10 parts
by mass or less (that is, 0 to 10 parts by mass), preferably 0.1 to
8 parts by mass, more preferably 0.2 to 5 parts by mass. When the
compounding amount is 10 parts by mass or less, there is no fear of
adversely affecting on the hardness of the cured material or of
enhancing the surface tackiness.
[0096] Further, as required, a liquid silicone component can be
added to an extent that can maintain the UV-curable adhesive
silicone composition of the present invention in a plastic solid
state or a semi-solid state at room temperature and does not allow
to be liquid. As such the liquid silicone component, a silicone
component having the viscosity at 25.degree. C. of 1 to 100,000
mPas is preferred. Examples thereof include vinylsiloxane,
hydrogensiloxane, alkoxysiloxane, hydroxysiloxane and mixtures
thereof. An addition amount of the liquid silicone component is
usually 50% by mass or less with respect to the UV-curable adhesive
silicone composition under the condition that the UV-curable
adhesive silicone composition maintains a plastic solid state or a
semi-solid state at room temperature.
UV-Curable Adhesive Silicone Composition Sheet
[0097] A UV-curable adhesive silicone composition sheet of the
present invention is obtained by forming the UV-curable adhesive
silicone composition of the invention into sheet-form.
[0098] As a method for processing the composition of the present
invention into sheet-form, for example, a film coater and a heat
press machine can be cited. When the composition is processed into
sheet-form by using these methods, for example, the composition is
sandwiched between a base film for pressurizing and a peeling film
and compression molded by using a heat press machine at a
temperature usually from 60 to 120.degree. C., preferably from 70
to 100.degree. C., under the pressure of 0.5 to 10 t/cm.sup.2,
preferably 1 to 7 ton/cm.sup.2, and for about 1 to about 30 min,
preferably 2 to 10 min.
[0099] Examples of the base films for pressurizing include a PET
film, a fluorine-based resin film, a polyethylene film, and a
polypropylene film, and examples of the peeling films include a
fluorine-based resin-coated PET film, a silicone resin-coated PET
film and a fluorine-based resin film can be cited.
[0100] A UV-curable adhesive silicone composition sheet formed from
such the UV-curable adhesive silicone composition is in a plastic
solid state or in a semi-solid state in an uncured state at room
temperature and easy to handle. Further, the UV-curable adhesive
silicone composition sheet can be readily adhered on a surface of a
semiconductor device such as an LED chip. Further, by curing only a
necessary portion with a UV-light source and a mask and by
dissolving and developing an unnecessary uncured portion with a
solvent, the sheet can form a cured layer only on a necessary
portion is formed. Further, when the UV-curable adhesive silicone
composition of the present invention contains a phosphor a cured
material (resin-cured layer) in which the phosphor is uniformly
dispersed and the dispersion state thereof is stable with time can
be obtained.
[0101] Examples of the UV light sources used in the present
invention include UV-LED lamps, high-pressure mercury lamps,
ultra-high pressure mercury lamps, low-pressure mercury lamps,
metal halide lamps, carbon ark lamps, and xenon lamps. A wavelength
of light being irradiated is 200 nm to 400 nm, preferably 250 to
400 nm, and any one of a single-wavelength light, a bright line
spectrum light and a continuous spectrum light can be used. An
exposure dose is, as an integral of light, 100 mJ/cm.sup.2 to
100,000 mJ/cm.sup.2, preferably 100 mJ/cm.sup.2 to 10,000
mJ/cm.sup.2, more preferably 100 mJ/cm.sup.2 to 5,000 mJ/cm.sup.2.
When the exposure dose is in the above range, the silicone resin
composition can be gelated by irradiating a light for a very short
time. The gelation in the present invention means a state where a
curing reaction of the resin composition partially proceed and the
resin composition become insoluble to a solvent.
[0102] The UV-curable adhesive silicone composition sheet of the
present invention is characterized in that, when a light having a
specified wavelength is irradiated, the silicone resin composition
is gelated. When a light having a specified wavelength is
irradiated for 0.5 to 10 sec, in particular, for 1 to 5 sec, for
example, on the silicone resin composition, thereafter, within 10
to 600 sec, particularly within 60 to 300 sec, the silicone resin
composition can be gelated.
[0103] Then, by heating, the gelated sheet can be completely cured.
Thereby, the resin composition can be cured without flowing during
heating, that is, with an initial shape maintained. The resin
composition is heat-cured at 25 to 200.degree. C., preferably 100
to 180.degree. C., for 3 min to 72 hr, preferably for 1 to 6 hr.
The heat-curing condition can be appropriately selected by
considering a balance of the working condition and the productivity
and the heat resistance of a light-emitting device and a
chassis.
Optical Semiconductor Apparatus and Manufacturing Method
Thereof
[0104] According to the present invention, a method for
manufacturing an optical semiconductor apparatus is provided, the
method including a step of disposing the UV-curable adhesive
silicone composition sheet on a surface of an optical semiconductor
device (an LED device, for example), a step of irradiating light,
and a step of, after that, heat-curing. According to the method, a
light-emitting apparatus having a coated LED device where a surface
of above-described LED device is covered with a resin-cured
layer.
[0105] In a method for manufacturing an optical semiconductor
apparatus, which uses such the adhesive silicone composition sheet,
the adhesive silicone composition sheet is used at a thickness of 1
to 500 .mu.m, preferably of 10 to 300 .mu.m. However, the thickness
is appropriately adjusted depending on the content and emission
efficiency of the phosphor, etc. A size of the sheet may well be
adjusted to a size of an LED device to be covered. After disposing
the sheet on a surface of the LED device, light is irradiated to
gel, after that, by heating, the sheet is completely cured. The
conditions of UV irradiation and heat-curing are as described
above, and, usually, after a first curing, a second curing is
conducted.
[0106] Thus, by using the adhesive silicone composition sheet of
the present invention, according to lithography that uses a UV
light source and a mask, by curing only a necessary portion and by
dissolving and developing an unnecessary uncured portion with a
solvent, a resin-cured layer can be readily formed only on a
necessary portion.
Cured Material (Resin Cured Layer)
[0107] The cured material obtained from the UV-curable adhesive
silicone composition and the UV-curable adhesive silicone
composition sheet are excellent in the heat resistance and light
transmittance. Further, the present invention can provide a cured
material having the light transmittance of 90% to 100%, in
particular, 95% to 100% of a light having a wavelength of 450 nm at
23.degree. C. in a layer state of a thickness of 1 mm. Accordingly,
the cured material can be preferably used as a sealing material,
etc. of optical semiconductor devices such as light-emitting diodes
(LEDs), organic electroluminescent devices (organic ELs), laser
diodes, and LED arrays. The reason why the transmittance is
obtained at a thickness of 1 mm is because when a lens is formed by
covering an LED chip, a thickness of the lens is about 1 mm.
[0108] An aspect of sealing an optical semiconductor device with
the cured material of the UV-curable adhesive silicone composition
of the present invention is not particularly limited. However, for
example, a method where the above silicone resin composition is
filled so that an optical semiconductor device disposed in a
chassis having an opening is covered, and UV-rays are irradiated to
heat to cure can be used. Further, a method where optical
semiconductor devices are mounted on a matrixed substrate and a
printing method, a transfer molding method, an injection molding
method, or a compression molding method is used to produce can be
used as well.
[0109] The silicone resin composition of the present invention is
in a plastic solid state or a semi-solid state at room temperature.
However, when the silicone resin composition is preheated at a
temperature of about 40 to 120.degree. C., preferably 80 to
100.degree. C., the resin composition is softened and melted and
becomes a property that allows to injection mold.
[0110] When the optical semiconductor device is covered and
protected by potting or injection method, the composition is
preferable to be in a liquid state when it is cast. Further, when
an optical semiconductor apparatus is produced by transfer molding,
the composition may be pelletized and used in molding.
[0111] When the transfer molding or injection molding is adopted,
it is preferable to mold at a temperature of 150 to 180.degree. C.
and under pressure of 20 to 50 kgf/cm.sup.2 for 1 to 5 min. When
the transfer molding or injection molding is used, after-cure
(secondary curing or post cure) may be conducted under the
condition of a temperature of 150 to 200.degree. C. for 1 to 4
hr.
[0112] The compression bonding can be usually applied at a
temperature from room temperature to 300.degree. C. or less, under
pressure of 10 MPa or less (usually 0.01 to 10 MPa), preferably 5
MPa or less (0.1 to 5 MPa, for example), particularly preferably
0.5 to 5 MPa. The curing is performed usually at a temperature from
50 to 200.degree. C., particularly, from 70 to 180.degree. C., and
for 1 to 30 min, particularly for 2 to 10 min. Further, the post
cure can be conducted at a temperature from 50 to 200.degree. C.,
particularly 70 to 180.degree. C. for 0.1 to 10 hr, particularly
for 1 to 4 hr.
EXAMPLES
[0113] Hereinafter, the present invention will be specifically
described with reference to Synthesis Examples, Examples and
Comparative Examples. However, the present invention is not limited
by the following Examples. Further, Ph denotes a phenyl group, Me
denotes a methyl group, and Vi denotes a vinyl group.
[0114] The weight average molecular weight referred in the present
invention indicates a weight average molecular weight based on a
polystyrene standard material according to gel permeation
chromatography (GPC) measured under the following condition.
[Measurement Condition]
[0115] ELUENT: THF [0116] Flow rate: 0.6 mL/min [0117] Detector:
Differential Refractive Index Detector (RI) [0118] Column: TSK
Guard Column Super H-L [0119] TSK-Gel Super H4000 (6.0 mm I.
D..times.15 cm.times.1) [0120] TSK-Gel Super H3000 (6.0 mm I.
D..times.15 cm.times.1) [0121] TSK-Gel Super H2000 (6.0 mm I.
D..times.15 cm.times.2) (all manufactured by Tosoh Corporation)
[0122] Column temperature: 40.degree. C. [0123] Injected amount of
sample: 20 .mu.L (THF solution of a concentration of 0.5% by
mass)
Synthesis Example 1
--Vinyl Group-Containing Organopolysiloxane Resin (A1)--
[0124] After dissolving 27 mol of organosilane represented as
PhSiCl.sub.3, 1 mol of
ClMe.sub.2SiO(Me.sub.2SiO).sub.33SiMe.sub.2Cl and 6 mol of
Me.sub.2ViSiCl in a toluene solvent, a toluene solution was dropped
in water and cohydrolyzed, further after cleaning with water, and
neutralizing and dewatering by alkali cleaning, by stripping the
solvent, a vinyl group-containing resin (A1) was synthesized.
[0125] In the resin, a constituent ratio of siloxane units which
constitute the resin and a structure represented by
[-SiMe.sub.2O-(Me.sub.2SiO).sub.33--SiMe.sub.2O.sub.2/2] is denoted
by a formula:
[PhSiO.sub.3/2].sub.0.27[--SiMe.sub.2O-(Me.sub.2SiO).sub.33--SiM-
e.sub.2O.sub.2/2].sub.0.01[Me.sub.2ViSiO.sub.1/2].sub.0.06. The
weight average molecular weight of the resin was 65,000, and the
melting point thereof was 58.degree. C.
Synthesis Example 2
--Hydrosilyl Group-Containing Organopolysiloxane Resin (B1)--
[0126] After dissolving 27 mol of organosilane represented as
PhSiCl.sub.3, 1 mol of
ClMe.sub.2SiO(Me.sub.2SiO).sub.33SiMe.sub.2Cl, and 6 mol of
Me.sub.2HSiCl in a toluene solvent, a toluene solution was dropped
in water and cohydrolyzed, further after cleaning with water, and
neutralizing and dewatering by alkali cleaning, by stripping the
solvent, a hydrosilyl group-containing resin (B1) was
synthesized.
[0127] In the resin, a constituent ratio of siloxane units which
constitute the resin and a structure represented by
[--SiMe.sub.2O-(Me.sub.2SiO).sub.33--SiMe.sub.2O.sub.2/2] is
denoted by a formula:
[PhSiO.sub.3/2].sub.0.27[--SiMe.sub.2O-(Me.sub.2SiO).sub.33--SiM-
e.sub.2O.sub.2/2].sub.0.01[Me.sub.2HSiO.sub.1/2].sub.0.06. The
weight average molecular weight of the resin was 56,000, and the
melting point thereof was 56.degree. C.
Synthesis Example 3
--Vinyl Group-Containing Organopolysiloxane Resin (A2)--
[0128] After dissolving 27 mol of organosilane represented as
PhSiCl.sub.3, 1 mol of
ClMe.sub.2SiO(Me.sub.2SiO).sub.33SiMe.sub.2Cl, and 9 mol of
Me.sub.2ViSiCl in a toluene solvent, a toluene solution was dropped
in water and cohydrolyzed, further after cleaning with water, and
neutralizing and dewatering by alkali cleaning, by stripping the
solvent, a vinyl group-containing resin (A2) was synthesized.
[0129] In the resin, a constituent ratio of siloxane units which
constitute the resin and a structure represented by
[--SiMe.sub.2O-(Me.sub.2SiO).sub.33--SiMe.sub.2O.sub.2/2] is
denoted by a formula:
[PhSiO.sub.3/2].sub.0.27[--SiMe.sub.2O-(Me.sub.2SiO).sub.33--SiM-
e.sub.2O.sub.2/2].sub.0.01[Me.sub.2ViSiO.sub.1/2].sub.0.09. The
weight average molecular weight of the resin was 62,000, and the
melting point thereof was 61.degree. C.
Synthesis Example 4
--Hydrosilyl Group-Containing Organopolysiloxane Resin (B2)--
[0130] After dissolving 27 mol of organosilane represented as
PhSiCl.sub.3, 1 mol of
ClMe.sub.2SiO(Me.sub.2SiO).sub.33SiMe.sub.2Cl, and 9 mol of
Me.sub.2HSiCl in a toluene solvent, a toluene solution was dropped
in water and cohydrolyzed, further after cleaning with water, and
neutralizing and dewatering by alkali cleaning, by stripping the
solvent, a hydrosilyl group-containing resin (B2) was
synthesized.
[0131] In the resin, a constituent ratio of siloxane units which
constitute the resin and a structure represented by
[--SiMe.sub.2O-(Me.sub.2SiO).sub.33--SiMe.sub.2O.sub.2/2] is
denoted by a formula:
[PhSiO.sub.3/2].sub.0.27[--SiMe.sub.2O-(Me.sub.2SiO).sub.33--SiM-
e.sub.2O.sub.2/2].sub.0.01[Me.sub.2HSiO.sub.1/2].sub.0.09. The
weight average molecular weight of the resin was 55,000, and the
melting point thereof was 54.degree. C.
Synthesis Example 5
--Vinyl Group-Containing Organopolysiloxane Resin (A3)--
[0132] After dissolving 27 mol of organosilane represented as
PhSiCl.sub.3, 1 mol of
ClMe.sub.2SiO(Me.sub.2SiO).sub.7SiMe.sub.2Cl, and 6 mol of
Me.sub.2ViSiCl in a toluene solvent, a toluene solution was dropped
in water and cohydrolyzed, further after cleaning with water, and
neutralizing and dewatering by alkali cleaning, by stripping the
solvent, a vinyl group-containing resin (A3) was synthesized.
[0133] In the resin, a constituent ratio of siloxane units which
constitute the resin and a structure represented by
[--SiMe.sub.2O-(Me.sub.2SiO).sub.7--SiMe.sub.2O.sub.2/2] is denoted
by a formula:
[PhSiO.sub.3/2].sub.0.27[--SiMe.sub.2O-(Me.sub.2SiO).sub.7--SiMe-
.sub.2O.sub.2/2].sub.0.01[Me.sub.2ViSiO.sub.1/2].sub.0.06. The
weight average molecular weight of the resin was 45,000, and the
melting point thereof was 56.degree. C.
Synthesis Example 6
--Hydrosilyl Group-Containing Organopolysiloxane Resin (B3)--
[0134] After dissolving 27 mol of organosilane represented as
PhSiCl.sub.3, 1 mol of
ClMe.sub.2SiO(Me.sub.2SiO).sub.7SiMe.sub.2Cl, and 6 mol of
Me.sub.2HSiCl in a toluene solvent, a toluene solution was dropped
in water and cohydrolyzed, further after cleaning with water, and
neutralizing and dewatering by alkali cleaning, by stripping the
solvent, a hydrosilyl group-containing resin (B3) was
synthesized.
[0135] In the resin, a constituent ratio of siloxane units which
constitute the resin and a structure represented by
[--SiMe.sub.2O-(Me.sub.2SiO).sub.7--SiMe.sub.2O.sub.2/2] is denoted
by a formula:
[PhSiO.sub.3/2].sub.0.27[--SiMe.sub.2O-(Me.sub.2SiO).sub.7--SiMe-
.sub.2O.sub.2/2].sub.0.01[Me.sub.2HSiO.sub.1/2].sub.0.06. The
weight average molecular weight of the resin was 42,000, and the
melting point thereof was 54.degree. C.
Synthesis Example 7
--Vinyl Group-Containing Organopolysiloxane Resin (A4)--
[0136] After dissolving 27 mol of organosilane represented as
PhSiCl.sub.3, 1 mol of
HOMe.sub.2SiO(Me.sub.2SiO).sub.98SiMe.sub.2OH, and 6 mol of
Me.sub.2ViSiCl in a toluene solvent, a toluene solution was dropped
in water and cohydrolyzed, further after cleaning with water, and
neutralizing and dewatering by alkali cleaning, by stripping the
solvent, a vinyl group-containing resin (A4) was synthesized.
[0137] In the resin, a constituent ratio of siloxane units which
constitute the resin and a structure represented by
[--SiMe.sub.2O-(Me.sub.2SiO).sub.98--SiMe.sub.2O.sub.2/2] is
denoted by a formula:
[PhSiO.sub.3/2].sub.0.27[--SiMe.sub.2O-(Me.sub.2SiO).sub.98--SiM-
e.sub.2O.sub.2/2].sub.0.01[Me.sub.2ViSiO.sub.1/2].sub.0.06. The
weight average molecular weight of the resin was 62,000, and the
melting point thereof was 60.degree. C.
Synthesis Example 8
--Hydrosilyl Group-Containing Organopolysiloxane Resin (B4)--
[0138] After dissolving 27 mol of organosilane represented as
PhSiCl.sub.3, 1 mol of
HOMe.sub.2SiO(Me.sub.2SiO).sub.98SiMe.sub.2OH, and 6 mol of
Me.sub.2HSiCl in a toluene solvent, a toluene solution was dropped
in water and cohydrolyzed, further after cleaning with water, and
neutralizing and dewatering by alkali cleaning, by stripping the
solvent, a hydrosilyl group-containing resin (B4) was
synthesized.
[0139] In the resin, a constituent ratio of siloxane units which
constitute the resin and a structure represented by
[--SiMe.sub.2O-(Me.sub.2SiO).sub.98--SiMe.sub.2O.sub.2/2] is
denoted by a formula:
[PhSiO.sub.3/2].sub.0.27[--SiMe.sub.2O(Me.sub.2SiO).sub.98--SiMe-
.sub.2O.sub.2/2].sub.0.01[Me.sub.2HSiO.sub.1/2].sub.0.06. The
weight average molecular weight of the resin was 60,000, and the
melting point thereof was 58.degree. C.
Example 1
[0140] With respect to 90 parts by mass of a composition where 189
g of the vinyl group-containing resin (A1) of the Synthesis Example
1, 189 g of the hydrosilyl group-containing resin (91) of Synthesis
Example 2, 0.2 g of acetylene alcohol-based ethynylcyclohexanol as
a reaction inhibitor, and 0.1 g of bis(acetylacetonato)platinum
(II) (manufactured by Tokyo Chemical Industry Co., Ltd.) were added
and dissolved in 10% toluene, 10 parts by mass of a phosphor (YAG)
having a particle size (average particle size) of 5 .mu.m were
further added and heated at 60.degree. C., cyclohexanone was
further added by 20% of the resin composition, the mixture was
thoroughly stirred with a planetary mixer, thereby a silicone resin
composition was prepared. The composition was a plastic solid in a
dried state at 25.degree. C.
1) Chromaticity Measurement
[0141] The composition was coated on a PTFE film 50 .mu.m thick
(base film for pressurizing) by a film coater at a blade of 100
.mu.m and dried at 100.degree. C. for 2 min to prepare a solid film
50 .mu.m thick. The solid film was further sandwiched between a
PTFE film 25 .mu.m thick (peeling film) and formed into sheet-form
having a thickness of 50 .mu.m by nipping with a roll.
[0142] The resulted composition sheet was cut together with the
peeling film into small chips. As is illustrated in FIG. 1, after
the resulted film chip was disposed on a GaN LED chip 1 so that a
composition side may come into contact with the LED chip, the
peeling film was removed. Then, via a photomask where only a
contact hole is covered, UV 365 nm was irradiated using a UV-LED
irradiator (type name: ZUV-C20H, manufactured by OMRON Corporation)
(integrated amount of light: 2000 mJ/cm.sup.2). Further, an uncured
portion was developed with IPA, this was further heated at
150.degree. C. for 60 min to cure, thereby a phosphor-containing
resin cured layer 2 was formed on the LED chip 1. By using the LED
chip 1 covered with the phosphor-containing resin cured layer 2
obtained like this, a light-emitting semiconductor (LED) apparatus
having a flip-chip structure such as illustrated in FIG. 1 was
prepared on a ceramic circuit board 3. In the figure, reference
numerals 4 and 5 respectively illustrate a wire contact portion and
a gold wire. By making every 3 LEDs emit, the chromaticity was
measured by using an LED Optical Characteristic Monitor (type name:
LE-3400, manufactured by Otsuka Electronics Co., Ltd.).
2) Mechanical Characteristics
[0143] The composition was compression molded by using a
compression molding machine, by using a UV-LED irradiator (type
name: ZUV-C20H, manufactured by OMRON Corporation), UV 365 nm
(integrated amount of light: 2000 mJ/cm.sup.2) was irradiated to
gelate, this was further cured at 150.degree. C. for 4 hr. The
resulted cured material was measured of the tensile strength (0.2
mm thick), the hardness (measured by using a type D spring tester)
and the breaking elongation (0.2 mm thick) in accordance with JIS K
6251 and JIS K 6253.
3) Tackiness of Surface
[0144] The tackiness of a surface of a cured material cured
similarly as the evaluation of the mechanical characteristics was
confirmed by touching with a finger. Further, the cured material
was embedded in commercially available silver powder (average
particle size: 5 .mu.m) and, after taking out, by blowing air,
whether the silver powder stuck on the surface like dust can be
removed or not was tested.
4) Dispersion Stability of Phosphor
[0145] The resin composition immediately after preparation was
charged in a recess having a diameter of 6 mm and a depth at a
center of 2 mm, which was formed on an alumina substrate, and, by
irradiating UV-rays and heat-curing in a manner similar to that in
the evaluation of the mechanical characteristics, a disc-like
molded product having a thickness of 2 mm and a diameter of 6 mm
was molded. From each of an upper superficial layer (thickness: 2
mm) and a lower superficial layer (thickness: 2 mm) of the molded
product, a part was cut out and heated at 800.degree. C. to ash,
the content (% by mass) of the phosphor in the resulted ash was
measured, and the contents in the upper portion and lower portion
were compared.
[0146] Further, after leaving to stand the composition in a
refrigerator at -20.degree. C. for 3 months, the composition was
molded in a manner similar to the above, and similarly, the
contents of phosphor in the upper portion and lower portion were
compared. In this manner, the dispersion stability of the phosphor
was measured.
[0147] These respective measurement results are shown in Table
1.
Example 2
[0148] With respect to 70 parts by mass of a composition where 189
g of the vinyl group-containing resin (A-2) of the Synthesis
Example 3, 189 g of the hydrosilyl group-containing resin (B-2) of
the Synthesis Example 4, 0.2 g of acetylene alcohol-based
ethynylcyclohexanol as a reaction inhibitor, and 0.1 g of
(methylcyclopentadienyl)trimethyl platinum (manufactured by Sigma
Aldrich Japan K. K.) were added and dissolved in 10% toluene, 30
parts by mass of a phosphor (YAG) having a particle size (average
particle size) of 5 .mu.m were further added, the mixture was
thoroughly stirred with a planetary mixer heated at 60.degree. C.,
thereby a silicone resin composition was prepared. The composition
was a plastic solid at 25.degree. C. The composition was evaluated
in a manner similar to Example 1. Results thereof are illustrated
in Table 1.
Example 3
[0149] A composition where 189 g of the vinyl group-containing
resin (A-1) of the Synthesis Example 1, 189 g of the hydrosilyl
group-containing resin (B-1) of the Synthesis Example 2, 0.2 g of
acetylene alcohol-based ethynylcyclohexanol as a reaction
inhibitor, and 0.1 g of (methylcyclopentadienyl)trimethyl platinum
(manufactured by Sigma Aldrich Japan K. K.) were added and
dissolved in 10% toluene was thoroughly stirred with a planetary
mixer heated at 60.degree. C., thereby a silicone resin composition
was prepared. The composition was a plastic solid at 25.degree. C.
The composition was evaluated and results thereof are illustrated
in Table 1.
Example 4
[0150] A composition where 189 g of the vinyl group-containing
resin (A-3) of the Synthesis Example 5, 189 g of the hydrosilyl
group-containing resin (B-3) of the Synthesis Example 6, 0.2 g of
acetylene alcohol-based ethynylcyclohexanol as a reaction
inhibitor, and 0.1 g of (methylcyclopentadienyl)trimethyl platinum
(manufactured by Sigma Aldrich Japan K. K.) were added and
dissolved in 10% toluene was thoroughly stirred with a planetary
mixer heated at 60.degree. C., thereby a silicone resin composition
was prepared. The composition was a plastic solid at 25.degree. C.
The composition was evaluated and results thereof are illustrated
in Table 1.
Example 5
[0151] A composition where 189 g of the vinyl group-containing
resin (A-4) of the Synthesis Example 7, 189 g of the hydrosilyl
group-containing resin (B-4) of the Synthesis Example 8, 0.2 g of
acetylene alcohol-based ethynylcyclohexanol as a reaction
inhibitor, and 0.1 g of (methylcyclopentadienyl)trimethyl platinum
(manufactured by Sigma Aldrich Japan K. K.) were added and
dissolved in 10% toluene was thoroughly stirred with a planetary
mixer heated at 60.degree. C., thereby a silicone resin composition
was prepared. The composition was a plastic solid at 25.degree. C.
The composition was evaluated and results thereof are illustrated
in Table 1.
Comparative Example 1
[0152] In place of the silicone resin composition prepared in the
Example 1, 90 parts by mass of a commercially available addition
reaction-curable silicone varnish, KJR-632 (trade name,
manufactured by Shin-Etsu Chemical Co., Ltd.) that does not contain
a linear diorganopolysiloxane chain architecture having the number
of repetitions of 5 to 300 and contains as a main component a vinyl
group-containing organopolysiloxane resin that is liquid at room
temperature, were used, further, after 10 parts by mass of the
phosphor (YAG) having a particle size of 5 .mu.m (average particle
size), which is the same as that of the Example 1, were added, a
composition obtained by thoroughly stirring with a planetary mixer
heated at 60.degree. C. was cured under the curing condition
described in Table 1, and the respective characteristics were
evaluated. Results are illustrated in Table 1.
Comparative Example 2
[0153] In place of the silicone resin composition prepared in the
Example 1, 70 parts by mass of a commercially available addition
reaction-curable silicone varnish, KJR-632L-1 (trade name,
manufactured by Shin-Etsu Chemical Co., Ltd.) that does not contain
a linear diorganopolysiloxane chain architecture having the number
of repetitive units of 5 to 300 and contains as a main component a
vinyl group-containing organopolysiloxane resin that is liquid at
room temperature, were used, further, after 30 parts by mass of the
phosphor (YAG) having a particle size of 5 .mu.m (average particle
size), which is the same as that of the Example 1, were added, a
composition obtained by thoroughly stirring with a planetary mixer
heated at 60.degree. C. was cured under the curing condition
described in Table 1, and the respective characteristics were
evaluated. Results are illustrated in Table 1.
TABLE-US-00001 TABLE 1 Comparative Comparative Example 1 Example 2
Example 3 Example 4 Example 5 Example 1 Example 2 SiH/SiVi.sup. 1
1.0 1.0 1.0 1.0 1.0 1.0 1.0 UV 2000 mJ 2000 mJ 2000 mJ 2000 mJ 2000
mJ -- -- irradiation possible possible possible possible possible
impossible impossible condition Processing of contact hole Curing
150.degree. C./ 150.degree. C./ 150.degree. C./ 150.degree. C./
150.degree. C./ 150.degree. C./ 150.degree. C./ condition 1 hr 1 hr
1 hr 1 hr 1 hr 1 hr 1 hr n x y x y x y x y x y x y x y Chroma- 1
0.310 0.310 0.310 0.310 -- -- -- -- -- -- 0.310 0.315 0.312 0.315
ticity 2 0.311 0.310 0.311 0.310 -- -- -- -- -- -- 0.305 0.321
0.314 0.310 3 0.310 0.310 0.310 0.310 -- -- -- -- -- -- 0.310 0.316
0.310 0.322 Tensile 8 8 7 7 8 1 1 strength (MPa) Hardness 55 60 40
40 38 75 80 Breaking 15 15 30 30 40 0 0 elongation (%) Adherence
None None None None None None None of dust due to surface tackiness
Dispersion No No -- -- -- Upper Upper of difference difference
portion portion phosphor (100/10) (100/10) (100/8) (100/25)
(immediate Lower Lower after) Wt portion portion ratio (100/12)
(100/33) Dispersion No No -- -- -- Upper Upper of difference
difference portion portion phosphor (100/10) (100/10) (100/2)
(100/3) (after 3 Lower Lower months) Wt portion portion ratio
(100/18) (100/50) (Note) .sup. 1: A mole ratio of hydrogen atoms
bonded to silicon atoms in a hydrosilyl group-containing resin with
respect to vinyl groups bonded to a silicon atom in a vinyl
group-containing resin.
[0154] The UV-curable adhesive silicone compositions according to
Examples 1 to 5 could be cured without allowing the composition to
flow during heat-curing but with an initial shape maintained.
Further, according to the compositions of Example 1 and Example 2,
a resin-cured layer in which the phosphor is uniformly dispersed
and the dispersion state thereof is stable with time could be
obtained. Still further, when a sheet formed from the composition
was used, only on a necessary portion, a resin-cured layer can be
formed according to lithography.
[0155] The present invention is not limited to the embodiments. The
embodiments are only illustrative examples. All of what has a
constitution essentially the same as that of a technical idea
described in the range of Claims of the invention and exerts the
same effect is included in the technical range of the
invention.
* * * * *