U.S. patent application number 13/881097 was filed with the patent office on 2013-09-12 for (meth)acrylate composition.
This patent application is currently assigned to Idemitsu Kosan Co. Ltd. The applicant listed for this patent is Takeshi Iwasaki, Yutaka Obata, Daichi Ogawa, Tomoaki Takebe. Invention is credited to Takeshi Iwasaki, Yutaka Obata, Daichi Ogawa, Tomoaki Takebe.
Application Number | 20130237660 13/881097 |
Document ID | / |
Family ID | 45993685 |
Filed Date | 2013-09-12 |
United States Patent
Application |
20130237660 |
Kind Code |
A1 |
Iwasaki; Takeshi ; et
al. |
September 12, 2013 |
(METH)ACRYLATE COMPOSITION
Abstract
Provided is a (meth)acrylate composition containing: (A) at
least one (meth)acrylate compound selected from the group
consisting of a (meth)acrylate-modified silicone oil, a
(meth)acrylate having a long-chain aliphatic hydrocarbon group, and
a polyalkylene glycol (meth)acrylate having number-average
molecular weight of not less than 400; (B) a (meth)acrylate
compound to which an alicyclic hydrocarbon group having 6 or more
carbon atoms is ester-linked; (C) (meth)acrylic acid or a
(meth)acrylate compound having a polar group; (D) a radical
polymerization initiator; and (E) a white pigment.
Inventors: |
Iwasaki; Takeshi; (Chiba,
JP) ; Ogawa; Daichi; (Chiba, JP) ; Obata;
Yutaka; (Chiba, JP) ; Takebe; Tomoaki; (Chiba,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Iwasaki; Takeshi
Ogawa; Daichi
Obata; Yutaka
Takebe; Tomoaki |
Chiba
Chiba
Chiba
Chiba |
|
JP
JP
JP
JP |
|
|
Assignee: |
Idemitsu Kosan Co. Ltd
Tokyo
JP
|
Family ID: |
45993685 |
Appl. No.: |
13/881097 |
Filed: |
October 19, 2011 |
PCT Filed: |
October 19, 2011 |
PCT NO: |
PCT/JP2011/074060 |
371 Date: |
April 23, 2013 |
Current U.S.
Class: |
524/531 ;
524/547; 524/548 |
Current CPC
Class: |
H01L 33/46 20130101;
C08K 2003/2241 20130101; H01L 2933/0033 20130101; C08F 220/12
20130101; C08F 224/00 20130101; C08F 230/08 20130101; C08K 3/22
20130101; C08F 290/062 20130101; H01L 33/60 20130101; C08F 220/32
20130101; C08F 220/04 20130101; C08F 230/02 20130101; C08F 220/10
20130101; C08F 290/062 20130101 |
Class at
Publication: |
524/531 ;
524/548; 524/547 |
International
Class: |
H01L 33/46 20060101
H01L033/46 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 25, 2010 |
JP |
2010 239001 |
Claims
1. A (meth)acrylate composition comprising: (A) at least one
(meth)acrylate compound selected from the group consisting of a
(meth)acrylate-modified silicone oil, a (meth)acrylate comprising a
long-chain aliphatic hydrocarbon group, and a polyalkylene glycol
(meth)acrylate having number-average molecular weight of not less
than 400, (B) a (meth)acrylate compound ester-linked to an
alicyclic hydrocarbon group having 6 or more carbon atoms, (C)
(meth)acrylic acid or a (meth)acrylate compound comprising a polar
group, (D) a radical polymerization initiator, and (E) a white
pigment.
2. The (meth)acrylate composition according to claim 1, wherein an
amount of the at least one (meth)acrylate compound (A) is from 5 to
90% by mass, an amount of the (meth)acrylate compound ester-linked
to an alicyclic hydrocarbon group (B) is from 5 to 90% by mass, and
an amount of the (meth)acrylic acid or (meth)acrylate compound (C)
is from 0.5 to 50% by mass, based on a totality of components (A),
(B) and (C), and an amount of the radical polymerization initiator
(D) is from 0.01 to 10 parts by mass and an amount of the white
pigment (E) is from 3 to 200 parts by mass, relative to 100 parts
by mass of a totality of the components (A), (B) and (C).
3. The (meth)acrylate composition according to claim 1, wherein the
at least one (meth)acrylate compound (A) is a (meth)acrylate having
an aliphatic hydrocarbon group with 12 or more carbon atoms, a
polyalkylene glycol (meth)acrylate having number-average molecular
weight of not less than 400, or any combination thereof.
4. The (meth)acrylate composition according to claim 1, wherein the
at least one (meth)acrylate compound (A) is a hydrogenated
polybutadiene di(meth)acrylate, hydrogenated polyisoprene
di(meth)acrylate, a polyethylene glycol di(meth)acrylate having
number-average molecular weight of not less than 400, or any
combination thereof.
5. The (meth)acrylate composition according to claim 1, wherein the
(meth)acrylate compound ester-linked to an alicyclic hydrocarbon
group (B) is a (meth)acrylate compound ester-linked with at least
one alicyclic hydrocarbon group selected from the group consisting
of adamantyl, norbornyl, isobornyl, dicyclopentanyl, and
cyclohexyl.
6. The (meth)acrylate composition according to claim 1, wherein the
(meth)acrylic acid or (meth)acrylate compound (C) is a
(meth)acrylate compound comprising a polar group selected from the
group consisting of hydroxyl, epoxy, glycidyl ether,
tetrahydrofurfuryl, isocyanate, carboxyl, alkoxysilyl, phosphate
ester, lactone, oxetane, and tetrahydropyranyl.
7. A cured product obtained by a process comprising curing the
(meth)acrylate composition according to claim 1.
8. A reflective material comprising the cured product according to
claim 7.
9. The reflective material according to claim 8, wherein the
reflective material is suitable for an optical semiconductor.
10. The (meth)acrylate composition according to claim 3, wherein
the (meth)acrylate compound ester-linked to an alicyclic
hydrocarbon group (B) is a (meth)acrylate compound ester-linked
with at least one alicyclic hydrocarbon group selected from the
group consisting of adamantyl, norbornyl, isobornyl,
dicyclopentanyl, and cyclohexyl.
11. The (meth)acrylate composition according to claim 3, wherein
the (meth)acrylic acid or (meth)acrylate compound (C) is a
(meth)acrylate compound comprising a polar group selected from the
group consisting of hydroxyl, epoxy, glycidyl ether,
tetrahydrofurfuryl, isocyanate, carboxyl, alkoxysilyl, phosphate
ester, lactone, oxetane, and tetrahydropyranyl.
12. The (meth)acrylate composition according to claim 10, wherein
the (meth)acrylic acid or (meth)acrylate compound (C) is a
(meth)acrylate compound comprising a polar group selected from the
group consisting of hydroxyl, epoxy, glycidyl ether,
tetrahydrofurfuryl, isocyanate, carboxyl, alkoxysilyl, phosphate
ester, lactone, oxetane, and tetrahydropyranyl.
Description
TECHNICAL FIELD
[0001] The present invention relates to a composition which
contains a (meth)acrylate compound, more specifically, to a
composition suitably used as a raw material of a reflective
material for an optical semiconductor and to a cured product
thereof.
BACKGROUND ART
[0002] Since 1990s, progress of a light-emitting diode (LED) is
remarkable whereby multicolor is progressing along with increase of
output power. In particular, a white LED is expected to be a next
generation light source to replace existing lamps such as a white
lamp, a halogen lamp, and an HID lamp. In fact, an LED is valued in
such characteristics as its long life, low power consumption, high
heat stability, and low-voltage drive. Therefore, it is used in a
display, a destination sign board, a car lamp, a signal light, an
emergency light, a cell phone, a video camera, and so on. Such
luminescent devices are usually manufactured by fixing an LED to a
concave-shaped reflective material formed of a synthetic resin
integrally molded with a lead frame and then by sealing it with a
sealant such as an epoxy resin and a silicone resin.
[0003] As the reflective material for the LED, a polyamide resin is
widely used nowadays. However, the reflectance decreases after a
long-term usage due to the deterioration of the resin caused by
increase of heat generation and optical intensity which is resulted
from enhanced output power of the LED. Therefore, a measure to
remedy this problem is desired.
[0004] To cope with this problem, for example, a reflective
material made using a silicone resin is proposed in Patent
Documents 1 to 3 and a reflective material made using an epoxy
resin is proposed in Patent Document 4. But none of them has yet
been used widely in practice. Especially when a silicone resin is
used, problems are concerned in association with evaporation of a
low molecular weight siloxane which may cause a contact malfunction
and penetration of water vapor into the luminescent device which
may cause damage to the light emitting element.
[0005] On the other hand, a reflective material made using a
(meth)acrylate resin is disclosed in Patent Documents 5 and 6. In
such reflective material, hollow particles are used as a filler to
increase reflectance in the ultraviolet light region. It is
disclosed that high reflectance in the visible light region can be
achieved by laminating the material with a material which has high
visible light reflectance.
CITATION LIST
Patent Literature
[0006] Patent Document 1: JP-A-2010-18786 [0007] Patent Document 2:
JP-A-2010-21533 [0008] Patent Document 3: JP-A-2010-106243 [0009]
Patent Document 4: JP-A-2010-47740 [0010] Patent Document 5:
JP-A-2008-231231 [0011] Patent Document 6: JP-A-2008-243892
SUMMARY OF INVENTION
Technical Problem
[0012] In view of the situation as mentioned above, a reflective
material having high reflectance in the visible light region and
the excellent adhesion with adjacent parts (lead frame and sealant)
without reflectance decrease even after a long-term usage is
desired.
[0013] Accordingly, the problem to be solved by the present
invention is to provide a (meth)acrylate composition which provides
a cured product having high reflectance in the visible light
region, the excellent heat resistance and light resistance, and the
excellent adhesion with adjacent parts, thereby suitably used as a
raw material of a reflective material for an optical
semiconductor.
Solution to Problem
[0014] The present inventors carried out an extensive investigation
and as a result, found that the above problem is solved by a
composition containing a certain acrylate compound. The present
invention was accomplished based on this finding.
[0015] That is, the present invention provides a (meth)acrylate
composition, a cured product, and a reflective material, as shown
below.
[1] A (meth)acrylate composition comprising:
[0016] (A) at least one (meth)acrylate compound selected from the
group consisting of a (meth)acrylate-modified silicone oil, a
(meth)acrylate having a long-chain aliphatic hydrocarbon group, and
a polyalkylene glycol (meth)acrylate having number-average
molecular weight of not less than 400,
[0017] (B) a (meth)acrylate compound to which an alicyclic
hydrocarbon group having 6 or more carbon atoms is
ester-linked,
[0018] (C) (meth)acrylic acid or a (meth)acrylate compound having a
polar group,
[0019] (D) a radical polymerization initiator, and
[0020] (E) a white pigment.
[2] The (meth)acrylate composition according to [1], wherein
[0021] the amount of the component (A) is 5 to 90% by mass, the
amount of the component (B) is 5 to 90% by mass, and the amount of
the component (C) is 0.5 to 50% by mass, based on totality of the
components (A), (B) and (C), and
[0022] the amount of the component (D) is 0.01 to 10 parts by mass
and the amount of the component (E) is 3 to 200 parts by mass,
relative to 100 parts by mass of totality of the components (A),
(B) and (C).
[3] The (meth)acrylate composition according to [1] or [2], wherein
the component (A) is a (meth)acrylate having an aliphatic
hydrocarbon group with 12 or more carbon atoms and/or a
polyalkylene glycol (meth)acrylate having number-average molecular
weight of not less than 400. [4] The (meth)acrylate composition
according to any of [1] to [3], wherein the component (A) is
hydrogenated polybutadiene di(meth)acrylate, hydrogenated
polyisoprene di(meth)acrylate, and/or polyethylene glycol
di(meth)acrylate having number-average molecular weight of not less
than 400. [5] The (meth)acrylate composition according to any of
[1] to [4], wherein the component (B) is a (meth)acrylate compound
which is ester-linked with at least one alicyclic hydrocarbon group
selected from the group consisting of adamantyl, norbornyl,
isobornyl, dicyclopentanyl, and cyclohexyl. [6] The (meth)acrylate
composition according to any of [1] to [5], wherein the component
(C) is a (meth)acrylate compound having a polar group selected from
the group consisting of hydroxyl, epoxy, glycidyl ether,
tetrahydrofurfuryl, isocyanate, carboxyl, alkoxysilyl, phosphate
ester, lactone, oxetane, and tetrahydropyranyl. [7] A cured product
obtained by curing the (meth)acrylate composition according to any
of [1] to [6]. [8] A reflective material made using the cured
product according to [7]. [9] The reflective material according to
[8], wherein the reflective material is a reflective material for
an optical semiconductor.
Advantageous Effects of Invention
[0023] The (meth)acrylate composition of the present invention
provides a cured product having high reflectance in the visible
light region with the excellent whiteness, the excellent heat
resistance and light resistance, and with less yellowing, and
having the excellent adhesion with adjacent parts (especially with
a lead frame), thereby suitably used as a raw material of a
reflective material for an optical semiconductor.
[0024] A reflective material made using the cured product obtained
by curing the (meth)acrylate composition of the present invention
does not decrease in its reflectance even after a long-term usage,
while having high reflectance in the visible light region and the
excellent adhesion with adjacent parts.
DESCRIPTION OF EMBODIMENTS
[(Meth)Acrylate Composition]
[0025] The (meth)acrylate composition of the present invention
contains:
[0026] (A) at least one (meth)acrylate compound selected from the
group consisting of a (meth)acrylate-modified silicone oil, a
(meth)acrylate having a long-chain aliphatic hydrocarbon group, and
a polyalkylene glycol (meth)acrylate having number-average
molecular weight of not less than 400,
[0027] (B) a (meth)acrylate compound to which an alicyclic
hydrocarbon group having 6 or more carbon atoms is
ester-linked,
[0028] (C) (meth)acrylic acid or a (meth)acrylate compound having a
polar group,
[0029] (D) a radical polymerization initiator, and
[0030] (E) a white pigment.
<Component (A)>
[0031] The component (A) used in the composition of the present
invention is at least one (meth)acrylate compound selected from the
group consisting of a (meth)acrylate-modified silicone oil, a
(meth)acrylate having a long-chain aliphatic hydrocarbon group, and
a polyalkylene glycol (meth)acrylate having number-average
molecular weight of not less than 400. Since the composition of the
present invention contains the component (A), mainly flexibility is
achieved so that formation of a crack may be suppressed.
((Meth)Acrylate-Modified Silicone Oil)
[0032] The (meth)acrylate-modified silicone oil used in the present
invention is a compound which has an acryl group and/or a methacryl
group at its terminal, and preferably contains a dialkyl
polysiloxane in the backbone. This (meth)acrylate-modified silicone
oil is a modified compound of dimethyl polysiloxane in many cases,
but all or a part of the alkyl groups in the dialkyl polysiloxane
backbone may be substituted with a phenyl group or an alkyl group
other than a methyl group in place of the methyl group. Examples of
the alkyl group other than the methyl group include an ethyl group
and a propyl group. As the commercially available products of such
compound, a single-end reactive silicone oil (for example,
X-22-174DX, X-22-2426, and X-22-2475), a dual-end reactive silicone
oil (for example, X-22-164A, X-22-164C, and X-22-164E) (all of the
above are tradenames and are manufactured by Shin-Etsu Chemical
Co., Ltd.), a methacrylate-modified silicone oil (for example,
BY16-152D, BY16-152, and BY16-152C) (all of the above are
tradenames and are manufactured by Dow Corning Toray Co., Ltd.),
and the like may be used.
[0033] In addition, as a (meth)acrylate-modified silicone oil, a
polydialkyl siloxane having an acryloxyalkyl terminal or a
methacryloxyalkyl terminal may be used. Specific examples thereof
include methacryloxypropyl-terminated polydimethylsiloxane,
(3-acryloxy-2-hydroxypropyl)-terminated polydimethylsiloxane, an
ABA type triblock copolymer of acryloxy-terminated ethylene oxide
dimethylsiloxane (A block) and ethylene oxide (B block), and
methacryloxpropyl-terminated branched polydimethylsiloxane.
[0034] Among them, in view of adhesion of the cured product,
(3-acryloxy-2-hydroxypropyl)-terminated polydimethylsiloxane and an
ABA type triblock copolymer of acryloxy-terminated ethylene oxide
dimethylsiloxane (A block) and ethylene oxide (B block) are
suitably used.
((Meth)Acrylate Having a Long-Chain Aliphatic Hydrocarbon
Group)
[0035] The (meth)acrylate having a long-chain aliphatic hydrocarbon
group used in the present invention is a compound having a
(meth)acrylate group bonded to a residue after a hydrogen atom is
removed from a long-chain aliphatic hydrocarbon compound.
[0036] As to the aliphatic hydrocarbon compound that can derive the
(meth)acrylate having a long-chain aliphatic hydrocarbon group used
in the present invention is preferably an alkane, in view of
adhesion of the cured product of the present invention, an alkane
having 12 or more carbon atoms being more preferable.
[0037] In view of adhesion of the cured product of the present
invention, the long-chain aliphatic hydrocarbon group is more
preferably an aliphatic hydrocarbon group having 12 or more carbon
atoms. By using the (meth)acrylate containing a long-chain
aliphatic hydrocarbon group having 12 or more carbon atoms as the
component (A), the composition of the present invention can provide
the cured product with the excellent adhesion.
[0038] In the (meth)acrylate having a long-chain aliphatic
hydrocarbon group used in the present invention, number of the
(meth)acrylate group is not particularly limited and one or a
plurality of the groups may be allowed. When there is one
(meth)acrylate group, the long-chain aliphatic hydrocarbon group is
preferably a long-chain alkyl group, more preferably an alkyl group
having 12 or more carbon atoms (preferably 12 to 24 carbon atoms,
more preferably 12 to 18 carbon atoms). When there are two
(meth)acrylate groups, the long-chain aliphatic hydrocarbon group
is preferably a long-chain alkylene group, more preferably an
alkylene group having 12 or more carbon atoms (preferably 12 to 24
carbon atoms, more preferably 12 to 18 carbon atoms).
[0039] Specific examples of the alkyl group having 12 or more
carbon atoms include dodecyl (including lauryl), tetradecyl,
hexadecyl, octadecyl (including stearyl), eicosyl, triacontyl, and
tetracontyl. Alternatively, the alkyl group having 12 or more
carbon atoms may be an alkyl group derived from a hydrogenated
product of polybutadiene, polyisoprene, and the like. Specific
examples of the alkylene group having 12 or more carbon atoms
include a divalent residue resulted by removing hydrogen atoms from
the foregoing alkyl groups.
[0040] Specific examples of the (meth)acrylate having a long-chain
aliphatic hydrocarbon group include an acryl or a methacryl
compound having a hydrogenated polybutadiene backbone or a
hydrogenated polyisoprene backbone, such as hydrogenated
polybutadiene di(meth)acrylate and hydrogenated polyisoprene
di(meth)acrylate, or stearyl methacrylate. Among them, in view of
adhesion of the cured product, hydrogenated polybutadiene
di(meth)acrylate and hydrogenated polyisoprene di(meth)acrylate are
preferable.
(Polyalkylene Glycol (Meth)Acrylate Having Number-Average Molecular
Weight of not Less than 400)
[0041] By using the polyalkylene glycol (meth)acrylate having
number-average molecular weight of not less than 400 as the
component (A), the composition of the present invention can provide
a cured product with the excellent toughness and adhesion. In the
polyalkylene glycol (meth)acrylate having number-average molecular
weight of not less than 400 used in the present invention, number
of the (meth)acrylate group is not particularly limited and one or
plurality of the groups may be allowed.
[0042] Specific examples of the polyalkylene glycol (meth)acrylate
having number-average molecular weight of not less than 400 include
polyethylene glycol di(meth)acrylate, polypropylene glycol
di(meth)acrylate, polybutylene glycol di(meth)acrylate, ethoxylated
trimethylolpropane tri(meth)acrylate, and ethoxylated
pentaerythritol tetra(meth)acrylate. Among them, in view of
toughness and adhesion, polyethylene glycol di(meth)acrylate is
preferable.
[0043] In view of toughness and adhesion as well as compatibility
with the component (B), the number-average molecular weight of such
compound is preferably 400 to 10,000, more preferably 450 to 5,000,
still more preferably 500 to 3,000.
[0044] In the present invention, as the component (A), at least one
selected from the (meth)acrylate-modified silicone oils, at least
one selected from the (meth)acrylates having a long-chain aliphatic
hydrocarbon group, or at least one selected from the polyalkylene
glycol (meth)acrylates having number-average molecular weight of
not less than 400 may be used. Alternatively, a combination of the
compounds appropriately selected from the (meth)acrylate-modified
silicone oils, the (meth)acrylates having a long-chain aliphatic
hydrocarbon group, and the polyalkylene glycol (meth)acrylates
having number-average molecular weight of not less than 400 may be
used.
[0045] Content of the component (A) in the composition of the
present invention is preferably 5 to 90% by mass, more preferably
15 to 80% by mass, still more preferably 20 to 70% by mass, based
on totality of the components (A), (B) and (C), in view of
toughness and adhesion.
<Component (B)>
[0046] The component (B) used in the composition of the present
invention is a (meth)acrylate compound to which an alicyclic
hydrocarbon group having 6 or more carbon atoms is
ester-linked.
[0047] As will be mentioned later, it is preferable that viscosity
of a mixed solution of the components (A) to (C) be higher in view
of dispersibility of a white pigment as the component (E). However,
if a highly viscous monomer (for example, hydrogenated
polybutadiene diacrylate) is used as the component (A), hardness of
the cured product decreases. Therefore, it is preferable to combine
it with a monomer which leads to a polymer having a high glass
transition temperature (Tg). Accordingly, in view of the
above-mentioned aspect, a (meth)acrylate having a substituent with
an alicyclic structure is preferred to a (meth)acrylate having a
substituent with a linear or branched structure as the component
(B), because the former leads to a polymer with higher Tg than the
latter.
[0048] Further, in the composition of the present invention, by
using the (meth)acrylate having an alicyclic hydrocarbon group with
6 or more carbon atoms as the component (B), the cured product
thereof is excellent in its hardness, heat resistance, and light
resistance. In addition, because the ester substituent is an
alicyclic hydrocarbon group not containing an aromatic group and
the like, deterioration thereof by an ultraviolet light is unlikely
to occur.
[0049] Specific examples of the alicyclic hydrocarbon group having
6 or more carbon atoms in such compounds include cyclohexyl,
2-decahydronaphthyl, adamantyl, 1-methyladamantyl,
2-methyladamantyl, biadamantyl, dimethyladamantyl, norbornyl,
1-methyl-norbornyl, 5,6-dimethyl-norbornyl, isobornyl,
tetracyclo[4.4.0.12,5.17,10]dodecyl,
9-methyl-tetracyclo[4.4.0.12,5.17,10]dodecyl, bornyl, and
dicyclopentanyl. Among them, in view of hardness, heat resistance,
and light resistance of the cured product thereof, cyclohexyl,
adamantyl, norbornyl, isobornyl, and dicyclopentanyl are
preferable, adamantyl being more preferable, and 1-methyladamantyl
being still more preferable.
[0050] Specific examples of the (meth)acrylate compound having the
alicyclic hydrocarbon group in the component (B) include cyclohexyl
(meth)acrylate, 1-adamantyl (meth)acrylate, norbornyl
(meth)acrylate, isobornyl (meth)acrylate, and dicyclopentanyl
(meth)acrylate. In the present invention, these (meth)acrylate
compounds may be used alone or in a combination of two or more
kinds as the component (B).
[0051] Meanwhile, since the viscosity of a monomer which leads to a
polymer having high Tg is generally low, it is preferable that a
monomer which leads to a polymer having a further higher Tg be used
to avoid decrease in viscosity of a mixed solution of the
components (A) to (C). By using the monomer which leads to a
polymer having a further higher Tg, smaller content thereof in the
composition may be used so that hardness of the cured product can
be made higher without decreasing viscosity of the solution. In
view of the above-mentioned aspect, a (meth)acrylate having an
adamantane structure which provides a polymer having high Tg is
preferable as the component (B), 1-adamantyl (meth)acrylate being
particularly preferable.
[0052] In view of harness, heat resistance, and light resistance,
content of the component (B) in the composition of the present
invention is preferably 5 to 90% by mass, more preferably 10 to 80%
by mass, still more preferably 20 to 70% by mass, based on totality
of the components (A), (B) and (C).
<Component (C)>
[0053] The component (C) used in the composition of the present
invention is (meth)acrylic acid or a (meth)acrylate compound having
a polar group. Since these compounds have a polar character,
adhesion with metal surface and the like having a polar character
is improved due to a formation of a hydrogen bond and the like by
incorporating the component (C) into the composition of the present
invention. In addition, wettability thereof is improved owing to
the presence of the polar group. Meanwhile, although an alkylene
glycol group may be involved in giving of adhesion, an alkylene
glycol (meth)acrylate shall not be included in the component
(C).
((Meth)Acrylate Compound Having a Polar Group)
[0054] As the (meth)acrylate compound having a polar group,
(meth)acrylate compounds having a substituent containing an atom
other than carbon and hydrogen ester-linked thereto are
exemplified. Examples of the substituent include hydroxyl, epoxy,
glycidyl ether, tetrahydrofurfuryl, isocyanate, carboxyl,
alkoxysilyl, phosphate ester, lactone, oxetane, tetrahydropyranyl,
and amino.
[0055] Specific examples of the (meth)acrylate compound having a
polar group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl
(meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl
(meth)acrylate (for example, tradename: 4-HBA, manufactured by
Nippon Kasei Chemical Co., Ltd.), cyclohexanedimethanol
mono(meth)acrylate (for example, tradename: CHMMA, manufactured by
Nippon Kasei Chemical Co., Ltd.), glycidyl (meth)acrylate,
4-hydroxybutyl acrylate glycidyl ether (for example, tradename:
4-HBAGE, manufactured by Nippon Kasei Chemical Co., Ltd.),
tetrahydrofurfuryl (meth)acrylate, 2-isocyanatoethyl
(meth)acrylate, 2-(meth)acryloyloxyethyl succinate,
2-(meth)acryloyloxyethyl hexahydrophthalate, 3-(meth)acryloxypropyl
trimethoxy silane, 3-(meth)acryloxypropyl methyl dimethoxy silane,
3-(meth)acryloxypropyl triethoxy silane, 3-(meth)acryloxypropyl
methyl diethoxy silane, 2-(meth)acryloyloxyethyl phosphate,
di(2-(meth)acryloyloxyethyl)phosphate, KAYAMER PM-21 (tradename,
manufactured by Nippon Kayaku Co., Ltd.), .gamma.-butyrolactone
(meth)acrylate, (meth)acrylic acid (3-methyl-3-oxetanyl),
(meth)acrylic acid (3-ethyl-3-oxetanyl), tetrahydrofurfuryl
(meth)acrylate, dimethylaminoethyl (meth)acrylate, and
diethylaminoethyl (meth)acrylate.
[0056] In the present invention, at least one selected from the
foregoing (meth)acrylic acids, or at least one selected from the
foregoing (meth)acrylate compounds having the polar group may be
used as the component (C), Alternatively, a combination of
appropriately selected compounds from the foregoing (meth)acrylic
acids and the foregoing (meth)acrylate compounds having the polar
group may be used.
[0057] Content of the component (C) in the composition of the
present invention is preferably 0.5 to 50% by mass, more preferably
1 to 40% by mass, still more preferably 3 to 20% by mass, based on
totality of the components (A), (B) and (C), in view of
adhesion.
<Component (D)>
[0058] The component (D) used in the composition of the present
invention is a radical polymerization initiator.
[0059] Although the radical polymerization initiator is not
particularly limited, specific examples thereof include ketone
peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides,
peroxyketals, alkyl peresters (peroxyesters), and peroxy
carbonates.
[0060] Specific examples of the ketone peroxide include methyl
ethyl ketone peroxide, methyl isobutyl ketone peroxide,
acetylacetone peroxide, cyclohexanone peroxide, and
methylcyclohexanone peroxide.
[0061] Specific examples of the hydroperoxide include
1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide,
t-butyl hydroperoxide, p-menthane hydroperoxide, and
diisopropylbenzene hydroperoxide.
[0062] Specific examples of the diacyl peroxide include
diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide,
dilauroyl peroxide, dibenzoyl peroxide, m-toluoyl benzoyl peroxide,
and succinic acid peroxide.
[0063] Specific examples of the dialkyl peroxide include dicumyl
peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane,
1,3-bis(t-butylperoxyisopropyl)hexane, t-butylcumyl peroxide,
di-t-butyl peroxide, di-t-hexyl peroxide, and
2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3.
[0064] Specific examples of the peroxyketal include
1,1-di-t-hexylperoxy-3,3,5-trimethylcyclohexane,
1,1-di-t-hexylperoxycyclohexane,
1,1-di-t-butylperoxy-2-methylcyclohexane,
1,1-di-t-butylperoxycyclohexane, 2,2-di(t-butylperoxy)butane, and
butyl 4,4-bis-t-butylperoxypentanoate.
[0065] Specific examples of the alkyl perester (peroxy esters)
include 1,1,3,3-tetramethylbutylperoxy neodecanoate,
.alpha.-cumylperoxy neodecanoate, t-butylperoxy neodecanoate,
t-hexylperoxy neodecanoate, t-butylperoxy neoheptanoate,
t-hexylperoxy pivalate, t-butylperoxy pivalate,
1,1,3,3-tetramethylbutylperoxy-2-ethyl hexanoate,
t-amylperoxy-2-ethyl hexanoate, t-butylperoxy-2-ethyl hexanoate,
t-butylperoxy isobutyrate, di-t-butylperoxy hexahydroterephthalate,
1,1,3,3-tetramethylbutylperoxy-3,5,5-trimethyl hexanoate,
t-amylperoxy-3,5,5-trimethyl hexanoate,
t-butylperoxy-3,5,5-trimethyl hexanoate, t-butylperoxy acetate,
t-butylperoxy benzoate, dibutylperoxytrimethyl adipate,
2,5-dimethyl-2,5-di-2-ethylhexanoylperoxyhexane,
t-hexylperoxy-2-ethyl hexanoate, t-hexylperoxy isopropyl
monocarbonate, t-butylperoxy laurate, t-butylperoxy isopropyl
monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, and
2,5-dimethyl-2,5-di-benzoylperoxyhexane.
[0066] Specific examples of the peroxy carbonate include
di-n-propylperoxy dicarbonate, diisopropylperoxy carbonate,
di-4-t-butylcyclohexylperoxy carbonate, di-2-ethylhexylperoxy
carbonate, di-sec-butylperoxy carbonate, di-3-methoxybutylperoxy
dicarbonate, di-2-ethylhexylperoxy dicarbonate, diisopropyloxy
dicarbonate, t-amylperoxy isopropyl carbonate, t-butylperoxy
isopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, and
1,6-bis(t-butylperoxycarboxyloxy)hexane.
[0067] Alternatively, a photo-radical polymerization initiator may
be used as the radical polymerization initiator of the component
(D). As the commercially available product of the radical
polymerization initiator, IRGACURE 651, IRGACURE 184, DAROCUR 1173,
IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE
379, DAROCUR TPO, IRGACURE 819, and IRGACURE 784 (all of these are
tradenames and are manufactured by BASF SE), and the like may be
used.
[0068] In the present invention, these radical polymerization
initiators of the component (D) may be used alone or in a
combination of two or more kinds.
[0069] Content of the component (D) in the composition of the
present invention is preferably 0.01 to 10 parts by mass, more
preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of
totality of the components (A), (B) and (C), in view of
polymerization reactivity.
<Component (E)>
[0070] The component (E) used in the composition of the present
invention is a white pigment. Incorporating the component (E) into
the composition of the present invention allows to make the cured
product white and to increase reflectance in the visible light
region.
[0071] Specific examples of the white pigment include titanium
dioxide, alumina, zirconium oxide, zinc sulfide, zinc oxide,
magnesium oxide, silica, potassium titanate, barium sulfate,
calcium carbonate, and silicone particle. Among them, titanium
dioxide is preferable in view of high reflectance and availability.
Among two crystal types of titanium dioxide, rutile and anatase,
the rutile type is preferable in the present invention because the
anatase type may cause deterioration of a resin due to its
photocatalytic function.
[0072] Average particle diameter of the white pigment in the
composition of the present invention is preferably in the range of
0.01 to 0.5 .mu.m, more preferably 0.1 to 0.4 still more preferably
0.15 to 0.3 .mu.m in view of dispersibility of the white
pigment.
[0073] Furthermore, the white pigment may be hollow particles. In
the case that the white pigment is hollow particles, a visible
light passing through an outer shell of the hollow particle is
reflected in the hollow part. Therefore, it is preferable that
difference between the refractive indexes of the constituent of the
hollow particle and gas present in the hollow particle be large in
order to increase reflectance in the hollow part. The gas present
in the hollow particle is usually air; but inert gas such as
nitrogen and argon may be used, or inside the hollow particle may
be vacuum.
[0074] In addition, the white pigment may be optionally
surface-treated with a silicon compound, an aluminum compound, an
organic substance, and so on. Examples of the treatment include an
alkylation treatment, a trimethylsilyl treatment, a silicone
treatment, and a treatment by a coupling agent. The white pigment
of the component (E) may be used alone or in a combination of two
or more kinds.
[0075] Content of the component (E) in the composition of the
present invention is preferably 1 to 200 parts by mass, more
preferably 3 to 150 parts by mass, still more preferably 5 to 100
parts by mass, relative to 100 parts by mass of totality of the
components (A), (B) and (C), in view of reflectance and mechanical
strength.
<Component (F)>
[0076] The composition of the present invention may contain a
(meth)acrylate compound other than the components (A) to (C) as the
component (F) within the range not adversely affecting the effect
of the present invention, in view of mechanical strength.
[0077] Specific examples of the (meth)acrylate compound of the
component (F) include ethylene glycol di(meth)acrylate, propylene
glycol di(meth)acrylate, 1,4-butanediol (meth)acrylate,
1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate,
neopentyldiol di(meth)acrylate, polyethylene glycol
di(meth)acrylate and polypropylene glycol di(meth)acrylate having
number-average molecular weight of less than 400, an
alkoxypolyalkylene glycol (meth)acrylate such as
methoxypolyethylene glycol methacrylate, ethylene oxide-modified
bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A
di(meth)acrylate, epichlorohydrin-modified bisphenol A
di(meth)acrylate, propylene oxide-modified glycerin
tri(meth)acrylate, trimethylolpropane tri(meth)acrylate,
ditrimethylolpropane tetra(meth)acrylate, dipentaerythrirol
hexa(meth)acrylate, tris(acryloyloxyethyl)isocyanurate, and
methoxypolyethylene glycol (meth)acrylate.
[0078] The foregoing (meth)acrylate compounds of the component (F)
may be used alone or in a combination of two or more kinds.
[0079] Content of the component (F) in the composition of the
present invention is preferably 100 or less parts by mass, more
preferably 50 or less parts by mass, relative to 100 parts by mass
of totality of the components (A), (B) and (C), in view of not
adversely affecting the effect of the present invention.
<Additive>
[0080] The composition of the present invention may further contain
any additives such as an antioxidant, a photo-stabilizer, a UV
absorber, a plasticizer, an inorganic filler, a coloring material,
an antistatic agent, a lubricating agent, a mold releasing agent,
and a flame retardant, within the range not adversely affecting the
effect of the present invention.
(Antioxidant)
[0081] Examples of the antioxidant include a phenol antioxidant, a
phosphorus antioxidant, a sulfur antioxidant, a vitamin
antioxidant, a lactone antioxidant, and an amine antioxidant.
[0082] Examples of the phenol antioxidant include
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane,
stearyl .beta.-(3,5-di-t-butyl-4-hydroxyphenyl) propionate ester,
1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene,
tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,
tris[(3,5-di-t-butyl-4-hydroxyphenyl)
propionyloxyethyl]isocyanurate, 2,6-di-t-butyl-4-methylphenol,
3,9-bis[1,1-dimethyl-2-{.beta.-(3-t-butyl-4-hydroxy-5-methylphenyl)propio-
nyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, and
tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate.
Commercially available products, for example, such as IRGANOX 1010,
IRGANOX 1076, IRGANOX 1330, IRGANOX 3114, IRGANOX 3125, and IRGANOX
3790 (all of them are manufactured by BASF SE); CYANOX 1790
(manufactured by Cyanamid Corp.); SUMILIZER BHT and SUMILIZER GA-80
(both are manufactured by Sumitomo Chemical Co., Ltd.) (all of the
above-mentioned are tradenames), and the like may be used.
[0083] Examples of the phosphorus antioxidant include
tris(2,4-di-t-butylphenyl) phosphite,
2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepi-
n6-yl]oxy]-N,N-bis[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,-
3,2]dioxaphosphepin-6-yl]oxy]-ethyl]ethanamine, cyclic
neopentanetetrayl bis(2,6-di-t-butyl-4-methylphenyl)phosphite, and
distearyl pentaerythritol diphosphite. Commercially available
products, for example such as IRGAFOS 168, IRGAFOS 12, and IRGAFOS
38 (these are manufactured by BASF SE); ADK STAB 329K, ADK STAB
PEP36, and ADK STAB PEP-8 (these are manufactured by ADEKA Corp.);
Sandstab P-EPQ (manufactured by Clariant SE); and Weston 618,
Weston 619G, and Weston-624 (these are manufactured by GE Company)
(all of the above-mentioned are tradenames), and the like may be
used.
[0084] Examples of the sulfur antioxidant include dilauryl
thiodipropionate, distearyl thiodipropionate, dimyristyl
thiodipropionate, lauryl stearyl thiodipropionate, pentaerythritol
tetrakis(3-dodecylthiopropionate), and pentaerythritol
tetrakis(3-laurylthiopropionate). Commercially available products,
for example, such as DSTP "Yoshitomi", DLTP "Yoshitomi", DLTOIB,
and DMTP "Yoshitomi" (all of them are manufactured by API Corp.);
Seenox 412S (manufactured by SHIPRO KASEI KAISHA, Ltd.); Cyanox
1212 (manufactured by Cyanamid Corp.); and SUMILIZER TP-D
(manufactured by Sumitomo Chemical Co., Ltd.) (all of the
above-mentioned are tradenames), and the like may be used.
[0085] Examples of the vitamin antioxidant include tocopherol and
2,5,7,8-tetramethyl-2-(4',8',12'-trimethyltridecyl)coumarone-6-ol
an example of the commercially available product including IRGANOX
E201 (tradename; manufactured by BASF SE).
[0086] Lactone antioxidant shown in JP-7-233160A and JP-7-247278A
may be used. Alternatively, HP-136 (tradename for
5,7-di-t-butyl-3-(3,4-dimethylphenyl)-3H-benzofurane-2-one,
manufactured by BASF SE) and the like may also be used.
[0087] Examples of the commercially available amine antioxidant
include IRGASTAB FS 042 (manufactured by BASF SE) and GENOX EP
(chemical name of dialkyl-N-methylamine oxide, manufactured by
Crompton Corp.) (all of the above-mentioned are tradenames).
[0088] These antioxidants may be used alone or in a combination of
two or more kinds.
[0089] Content of the antioxidant in the composition of the present
invention is preferably 0.005 to 5 parts by mass, more preferably
0.02 to 2 parts by mass, relative to 100 parts by mass of totality
of the components (A), (B) and (C), in view of not adversely
affecting the effect of the present invention.
(Photo-Stabilizer)
[0090] Although any photo-stabilizers may be used, a hindered amine
photo-stabilizer is preferable. Specific examples thereof include
ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-68, LA-77, LA-82,
LA-87, and LA-94 (all of them are manufactured by ADEKA Corp.);
Tinuvin 123, 144, 440, 662, 765, and 770DF, and Chimassorb 2020,
119, and 944 (all of them are manufactured by BASF SE); Hostavin
N30 (manufactured by Hoechst SE); Cyasorb UV-3346 and UV-3526 (both
are manufactured by Cytech, Inc.); Uval 299 (manufactured by GLC
Corp.); and Sanduvor PR-31 (manufactured by Clariant SE) (all of
the above-mentioned are tradenames).
[0091] These photo-stabilizers may be used alone or in a
combination of two or more kinds.
[0092] Content of the photo-stabilizer in the composition of the
present invention is preferably 0.005 to 5 parts by mass, more
preferably 0.002 to 2 parts by mass, relative to 100 parts by mass
of totality of the components (A), (B) and (C), in view of not
adversely affecting the effect of the present invention.
[Method for Producing (Meth)Acrylate Composition]
[0093] The composition of the present invention may be obtained by
mixing the foregoing component (A), component (B), component (C),
component (D), component (E) and optionally component (F) and an
additive.
[0094] The (meth)acrylate compounds of the components (A) to (C)
are liquid; and therefore, when the white pigment of the component
(E) is mixed thereinto for dispersion, the white pigment tends to
precipitate if viscosity of the liquid is low, thereby causing
inhomogeneous color in the cured product by precipitation of the
white pigment prior to curing of the composition. This is
undesirable for the performance of the reflective material. In view
of this, viscosity of the mixture solution of the components (A) to
(C) is preferably 50 mPas or higher, more preferably 100 mPas or
higher, still more preferably 200 mPas or higher. Since a monomer
with high viscosity (for example, hydrogenated polybutadiene
diacrylate) is contained in the component (A) used in the present
invention, viscosity of the liquid may be increased by using such a
compound. If a monomer with high viscosity is not used, the problem
may be addressed by stirring the monomer composition in the vessel
during the time of molding such as transfer molding or press
molding as will be mentioned later.
[0095] Order of addition of each component may be determined as
needed within the range not adversely affecting the effect of the
present invention. For example, it is preferable that the white
pigment of the component (E) be mixed and dispersed in the mixture
after preparing a mixed solution of the components (A) to (D) and
optionally the component (F) and an additive, thereby preparing the
composition, in view of uniformly dispersing the white pigment of
the component (E) in the composition.
[0096] Since the white pigment is more difficult to disperse in a
more viscous solution, a rough surface or decrease in mechanical
strength of the cured product may occur due to the presence of
agglomerated particles. In this case, the white pigment may be well
dispersed in a highly viscous solution by first adding the white
pigment of the component (E) to less viscous components among the
components (A) to (C) to prepare a mixed solution, followed by
adding and mixing the more viscous component (A) thereinto.
[0097] A means to mix the respective components is not particularly
limited and any stirrers (mixers) may be used.
[0098] Meanwhile, a mixer having a high mixing performance
generally generates heat during the time of mixing so that curing
may take place during mixing when the mixer is used with addition
of the component (D). Therefore, in the case that a mixer having a
high mixing performance is used, it is preferable that, after the
components (A) to (C) and the component (E) are mixed by the mixer
having a high mixing performance, the component (D) be added and
mixed by stirring to the extent not to generate heat.
[Cured Product and Reflective Material]
[0099] The composition of the present invention gives a cured
product by a radical polymerization reaction by heating the
composition above the temperature to generate a radical from the
component (D) (in the case of a photo-radical polymerization
initiator, by irradiation with a light having a sufficient energy
to generate a radical). Conditions for curing may be determined as
needed by considering decomposition characteristics and so on of
the polymerization initiator. The cured product obtained by curing
the composition of the present invention is used suitably as a
material for a reflective material.
[0100] The reflective material of the present invention may be
produced by transfer molding or press molding by using the
polymerizable composition of the present invention.
[0101] In the case of transfer molding, molding may be done by
using a transfer molding machine with the conditions of, for
example, molding pressure of 5 to 20 N/mm.sup.2, molding
temperature of 120 to 190.degree. C., and molding time of 30 to 500
seconds; preferably molding temperature of 150 to 185.degree. C.
and molding time of 30 to 180 seconds. In the case of press
molding, molding may be done by using a compression molding machine
with the conditions of, for example, molding temperature of 120 to
190.degree. C. and molding time of 30 to 600 seconds; preferably
molding temperature of 130 to 160.degree. C. and molding time of 30
to 300 seconds. In any of the molding methods, post-curing may be
done, for example, at 150 to 185.degree. C. for 0.5 to 24
hours.
[0102] Alternatively, a molded article may be obtained by liquid
resin injection molding, insert molding, potting processing,
coating processing, and the like. In addition, a molded article may
be obtained by a method similar to molding of a photo-curable
resin, such as by UV-cure molding. When the polymerizable
composition of the present invention is molded by transfer molding,
press molding, liquid resin injection molding, insert molding,
potting processing, coating processing, and the like,
pre-polymerization may be done.
[0103] The reflective material of the present invention has the
excellent adhesion with adjacent parts such as a lead frame and a
sealant. Breaking stress of the reflective material of the present
invention measured by the adhesion test described in EXAMPLES is
preferably 5.0 MPa or more, more preferably 5.5 MPa or more, still
more preferably 7.0 MPa or more.
[0104] Meanwhile, adhesion with a sealant may be further enhanced
by an activating the surface of the article with a treatment such
as UV-irradiation, ozone exposure, plasma exposure, corona
discharge, high-pressure discharge, and the like, after molding the
reflective material of the present invention.
[0105] The reflective material of the present invention has high
reflectance in the visible light region with small decrease of
reflectance even after a long-term usage. Photo-reflectance of the
reflective material of the present invention at 450 nm wavelength
is, as its initial value, preferably 85% or more, more preferably
90% or more, still more preferably 95% or more; and after the
deterioration test at 150.degree. C. for 1,000 hours,
photo-reflectance of preferably 80% or more, more preferably 85% or
more, still more preferably 90% or more may be accomplished.
Meanwhile, photo-reflectance is measured by the method described in
EXAMPLES.
[0106] The reflective material of the present invention may be used
for a lamp reflector of a liquid crystal display, a showcase
reflective board, a reflective board of various illumination
apparatuses, a reflective material for LED, and so on, being
especially suitable for a reflective material for an optical
semiconductor.
EXAMPLES
[0107] Then, the present invention will be explained in more detail
by EXAMPLES; however, the present invention is not restricted at
all by these EXAMPLES.
[0108] Methods for evaluation of physical properties of the cured
product obtained in each of examples and comparative examples are
as follows.
(1) Adhesion Test
[0109] Two silver-plated metal plates widely used in a lead frame
(width of 20 mm, length of 80 mm, and thickness of 0.3 mm) were
piled up with overlapping of 2 cm. Onto this overlapped area was
applied each composition solution obtained by Examples or
Comparative Examples and was cured to obtain a test piece. Then,
the tensile shear adhesion strength thereof (breaking stress; the
maximum stress at the time of breaking) was measured according to
JIS K6850. As the measurement instrument, a tensile tester
Autograph equipped with a controlled temperature bath (tradename:
AG-10, manufactured by Shimadzu Corp.) was used.
<Measurement Conditions>
[0110] Measurement temperature: 23.degree. C., humidity: 50% RH,
tensile speed: 20 mm/minute, and tensile load: 10 kN (load
cell)
(2) Measurement of Photo-Reflectance
[0111] Photo-reflectance of the cured test piece was measured with
an autographic spectrophotometer (tradename: UV-2400 PC,
manufactured by Shimadzu Corp.) equipped with a large multipurpose
chamber unit for a test piece (tradename: MPC-2200, manufactured by
Shimadzu Corp.). After the initial value of photo-reflectance of
the cured test piece was measured, photo-reflectance of the cured
test piece after being heated in an oven at 150.degree. C. for a
prescribed time period was measured.
(3) LED Burn-in Test (Evaluation of Heat Resistance and Light
Resistance)
[0112] The cured test piece was fixed on an LED package mounted
with a blue LED (tradename: OBL-CH2424, manufactured by GeneLite
Inc.). The LED was allowed to emit light by applying an electric
current of 150 mA for one week at an environmental temperature of
60.degree. C. Surface of the cured test piece exposed to the LED
light was visually checked and evaluated according to the following
criteria.
[0113] Good: no color change
[0114] Poor: Color of the irradiated surface changed to brown.
Example 1
[0115] Materials used in respective components were: 6.5 g of
hydrogenated polyisoprene diacrylate (tradename: SPIDA,
manufactured by Osaka Organic Chemical Industry, Ltd.) as the
component (A) ((meth)acrylate having a long-chain aliphatic
hydrocarbon group); 3.5 g of 1-adamantyl methacrylate (tradename:
Adamantate M-104, manufactured by Idemitsu Kosan Co., Ltd.) as the
component (B); 0.5 g of glycidyl methacrylate (manufactured by Wako
Pure Chemical Industries, Ltd.) as the component (C); 0.1 g of
1,1-bis(t-hexylperoxy)cyclohexane (tradename: Perhexa HC,
manufactured by NOF Corp.) as the component (D); and 1 g of
titanium dioxide (tradename: Tipaque PC-3, average particle
diameter of 0.21 .mu.m, manufactured by Ishihara Sangyo Kaisha,
Ltd.) as the component (E). Firstly, the component (E) was added to
the less viscous components (B), (C), and (D) and mixed using a
planetary centrifugal mixer (tradename: Awatori-Rentaro,
manufactured by Thinky Corp.). Then, the more viscous component (A)
was added to the mixture, and the resulting mixture was stirred
using the same mixer to obtain a composition.
[0116] This composition was applied on a metal plate for the
adhesion test; and then, this was piled up on another plate. After
heating at 150.degree. C. for one hour in an oven, the plate was
cooled to room temperature to obtain a cured test piece for the
adhesion test. Result of the adhesion test is shown in Table 1.
Example 2
[0117] A composition and a cured test piece were obtained by the
method similar to that in Example 1 except that the amount of the
component (C) was changed to 1 g. Result of the adhesion test is
shown in Table 1.
Example 3
[0118] A composition and a cured test piece were obtained by the
method similar to that in Example 1 except that the amount of the
component (C) was changed to 2 g. Result of the adhesion test is
shown in Table 1.
Example 4
[0119] A composition and a cured test piece were obtained by the
method similar to that in Example 1 except that 1 g of
4-hydroxybutyl acrylate (tradename: 4HBA, manufactured by Nippon
Kasei Chemical Co., Ltd.) was used as the component (C). Result of
the adhesion test is shown in Table 1.
Comparative Example 1
[0120] A composition and a cured test piece were obtained by the
method similar to that in Example 1 except that the component (C)
was not used. Result of the adhesion test is shown in Table 1.
TABLE-US-00001 TABLE 1 Comparative Example 1 Example 2 Example 3
Example 4 Example 1 Component (A) Hydrogenated polyisoprene
diacrylate (g) 6.5 6.5 6.5 6.5 6.5 (% by mass) *1 61.9% 59.1% 54.2%
59.1% 65.0% Component (B) 1-Adamantyl methacrylate (g) 3.5 3.5 3.5
3.5 3.5 (% by mass) *1 33.3% 31.8% 29.2% 31.8% 35.0% Component (C)
Glycidyl methacrylate (g) 0.5 1 2 -- -- (% by mass) *1 4.8% 9.1%
16.6% -- -- 4-Hydroxybutyl acrylate (g) -- -- -- 1 -- (% by mass)
*1 -- -- -- 9.1% -- Component (D) 1,1-Bis(t-hexylperoxy)cyclohexane
(g) 0.1 0.1 0.1 0.1 0.1 (parts by mass)*2 1.0 0.9 0.8 0.9 1.0
Component (E) Titanium dioxide (g) 1 1 1 1 1 (parts by mass)*2 9.5
9.1 8.3 9.1 10.0 Adhesion Stress at maximum point (MPa) 5.5 7.4 10
5.8 3.3 *1: % by mass based on totality of the components (A), (B)
and (C) *2parts by mass relative to 100 parts by mass of totality
of the components (A), (B) and (C)
[0121] As shown in Table 1, it was observed that the component (C)
is effective in adhesion with the lead frame material. Accordingly,
it was found that the composition of the present invention provides
a cured product having the excellent adhesion with adjacent parts
(especially with the lead frame).
Example 5
[0122] Materials used in respective components were: 15 g of lauryl
acrylate ((meth)acrylate having a long-chain aliphatic hydrocarbon
group; tradename: SR-335, manufactured by Sartomer, LLC) and 5 g of
polyethylene glycol #400 dimethacrylate (polyalkyleneglycol
(meth)acrylate having number-average molecular weight of not less
than 400; tradename: NK Ester 9G (molecular weight: 536),
manufactured by Shin-Nakamura Chemical Co., Ltd.) as the component
(A); 25 g of 1-adamantyl methacrylate (tradename: Adamantate M-104,
manufactured by Idemitsu Kosan Co., Ltd.) as the component (B); 5 g
of glycidyl methacrylate (manufactured by Wako Pure Chemical
Industries, Ltd.) as the component (C); 0.5 g of
1,1-bis(t-hexylperoxy)cyclohexane (tradename: Perhexa HC,
manufactured by NOF Corp.) as the component (D), and 0.25 g of
antioxidant (tradename: IRGANOX 3114, chemical name:
tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, manufactured by
BASF SE); and 75 g of titanium dioxide (average particle diameter:
0.21 .mu.m, tradename: Tipaque PC-3, manufactured by Ishihara
Sangyo Kaisha, Ltd.) as the component (E). In this Example, because
a highly viscous monomer is not contained, the components (A) to
(D) and the antioxidant were mixed using a planetary centrifugal
mixer (tradename: Awatori-Rentaro, manufactured by Thinky Corp.);
and then, the component (E) was added to the mixture, and the
resulting mixture was stirred using the same mixer to obtain a
composition.
[0123] Then, a spacer having 3 mm thickness made of
tetrafluoroethylene and an aluminum plate having 3 mm thickness
were inserted between two steel plates in such a manner that the
aluminum plate may be tucked in between the steel plate and the
spacer to make a cell. The above-mentioned composition was poured
into the space of the cell, and the cell was heated in an oven at
150.degree. C. for one hour, and then cooled to room temperature.
The steel plates, the spacer, and the aluminum plate were removed
to obtain a cured test piece composed of the composition.
Measurement of the photo-reflectance and the LED burn-in test were
carried out using the cured test piece according to the methods
mentioned above. The results are shown in Table 2.
Example 6
[0124] Materials used in respective components were: 25 g of
hydrogenated polybutadiene diacrylate (tradename: SPBDA-S30,
manufactured by Osaka Organic Chemical Industry, Ltd.) as the
component (A); 22.5 g of 1-adamantyl methacrylate (tradename:
Adamantate M-104, manufactured by Idemitsu Kosan Co., Ltd.) as the
component (B); 2.5 g of glycidyl methacrylate (manufactured by Wako
Pure Chemical Industries, Ltd.) as the component (C); 1 g of
1,1-bis(t-hexylperoxy)cyclohexane (tradename: Perhexa HC,
manufactured by NOF Corp.) as the component (D), and 0.25 g of
Sumilizer GA-80 (tradename of
3,9-bis[1,1-dimethyl-2-{.beta.-(3-t-butyl-4-hydroxy-5-methylphenyl)propio-
nyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undececane, manufactured
by Sumitomo Chemical Co., Ltd.) and 0.25 g of Sumilizer TP-D
(tradename of pentaerythritol tetrakis(3-laurylthiopropionate),
manufactured by Sumitomo Chemical Co., Ltd.) as the antioxidants;
and 35 g of titanium dioxide (tradename: Tipaque PC-3, manufactured
by Ishihara Sangyo Kaisha, Ltd.) as the component (E). Firstly, the
component (E) was added to the less viscous components (B) to (D)
and antioxidants and mixed using a planetary centrifugal mixer
(tradename: Awatori-Rentaro, manufactured by Thinky Corp.). Then,
the more viscous component (A) was added to the mixture, and the
resulting mixture was stirred using the same mixer to obtain a
composition.
[0125] A cured test piece was obtained by the method similar to
that in Example 5 except that this composition was used; and then,
measurement of the photo-reflectance and the LED burn-in test were
carried out. The results are shown in Table 2.
Example 7
[0126] Materials used in respective components were: 25 g of
hydrogenated polyisoprene diacrylate (tradename: SPIDA,
manufactured by Osaka Organic Chemical Industry, Ltd.) as the
component (A); 22.5 g of 1-adamantyl methacrylate (tradename:
Adamantate M-104, manufactured by Idemitsu Kosan Co., Ltd.) as the
component (B); 2.5 g of glycidyl methacrylate (manufactured by Wako
Pure Chemical Industries, Ltd.) as the component (C); 1 g of
1,1-bis(t-hexylperoxy)cyclohexane (tradename: Perhexa HC,
manufactured by NOF Corp.) as the component (D), and 0.25 g of
Sumilizer GA-80 (tradename, manufactured by Sumitomo Chemical Co.,
Ltd.) and 0.25 g of Sumilizer TP-D (tradename, manufactured by
Sumitomo Chemical Co., Ltd.) as the antioxidants; and 5 g of
titanium dioxide (tradename: Tipaque PC-3, manufactured by Ishihara
Sangyo Kaisha, Ltd.) as the component (E). These compounds were
mixed in the same order as Example 6 to obtain a composition.
[0127] A cured test piece was obtained by the method similar to
that in Example 5 except that this composition was used; and then,
measurement of the photo-reflectance and the LED burn-in test were
carried out. The results are shown in Table 2.
Example 8
[0128] A composition was obtained by the method similar to that in
Example 7 except that 12.5 g of the component (E) was used in
Example 7.
[0129] A cured test piece was obtained by the method similar to
that in Example 5 except that this composition was used; and then,
measurement of the photo-reflectance and the LED burn-in test were
carried out. The results are shown in Table 2.
Example 9
[0130] Materials used in respective components were: 15 g of lauryl
acrylate (tradename: SR335, manufactured by Sartomer, LLC) and 10 g
of ethoxylated (9) trimethylolpropane triacrylate (tradename:
SR-502, molecular weight: 692, manufactured by Sartomer, LLC) as
the component (A); 22.5 g of 1-adamantyl methacrylate (tradename:
Adamantate M-104, manufactured by Idemitsu Kosan Co., Ltd.) as the
component (B); 2.5 g of glycidyl methacrylate (manufactured by Wako
Pure Chemical Industries, Ltd.) as the component (C); 0.5 g of
1,1-bis(t-hexylperoxy)cyclohexane (tradename: Perhexa HC,
manufactured by NOF Corp.) as the component (D), and 0.25 g of
Sumilizer GA-80 (tradename, manufactured by Sumitomo Chemical Co.,
Ltd.) and 0.25 g of Sumilizer TP-D (tradename, manufactured by
Sumitomo Chemical Co., Ltd.) as the antioxidants; and 50 g of
titanium dioxide (tradename of Tipaque PC-3, manufactured by
Ishihara Sangyo Kaisha, Ltd.) as the component (E). These compounds
were mixed in the same order as Example 5 to obtain a
composition.
[0131] A cured test piece was obtained by the method similar to
that in Example 5 except that this composition was used; and then,
measurement of the photo-reflectance and the LED burn-in test were
carried out. The results are shown in Table 2.
Example 10
[0132] Materials used in respective components were: 25 g of
dual-end reactive silicone oil (tradename: X-22-164E, manufactured
by Shin-Etsu Chemical Co., Ltd.) as the component (A); 22.5 g of
1-adamantyl methacrylate (tradename: Adamantate M-104, manufactured
by Idemitsu Kosan Co., Ltd.) as the component (B); 2.5 g of
glycidyl methacrylate (manufactured by Wako Pure Chemical
Industries, Ltd.) as the component (C); 0.5 g of
1,1-bis(t-hexylperoxy)cyclohexane (tradename: Perhexa HC,
manufactured by NOF Corp.) as the component (D), and 0.25 g of
Sumilizer GA-80 (tradename, manufactured by Sumitomo Chemical Co.,
Ltd.) and 0.25 g of Sumilizer TP-D (tradename, manufactured by
Sumitomo Chemical Co., Ltd.) as the antioxidants; and 5 g of
titanium dioxide (tradename of Tipaque PC-3, manufactured by
Ishihara Sangyo Kaisha, Ltd.) as the component (E). These compounds
were mixed in the same order as Example 6 to obtain a
composition.
[0133] A cured test piece was obtained by the method similar to
that in Example 5 except that this composition was used; and then,
measurement of the photo-reflectance and the LED burn-in test were
carried out. The results are shown in Table 2.
Comparative Example 2
[0134] Measurement of the photo-reflectance and the LED burn-in
test were carried out using a plate of white polyphthalamide resin
(tradename: AMODEL A-4122NL, manufactured by Solvay Advanced
Polymers, LLC). The results are shown in Table 2.
Comparative Example 3
[0135] Materials used in respective components were: 2.5 g of
hydrogenated polyisoprene diacrylate (tradename: SPIDA,
manufactured by Osaka Organic Chemical Industry, Ltd.) as the
component (A); 46.5 g of 1-adamantyl methacrylate (tradename:
Adamantate M-104, manufactured by Idemitsu Kosan Co., Ltd.) as the
component (B); 1.0 g of glycidyl methacrylate (manufactured by Wako
Pure Chemical Industries, Ltd.) as the component (C); 1 g of
1,1-bis(t-hexylperoxy)cyclohexane (tradename: Perhexa HC,
manufactured by NOF Corp.) as the component (D), and 0.25 g of
Sumilizer GA-80 (tradename, manufactured by Sumitomo Chemical Co.,
Ltd.) and 0.25 g of Sumilizer TP-D (tradename, manufactured by
Sumitomo Chemical Co., Ltd.) as the antioxidants; and 5 g of
titanium dioxide (tradename: Tipaque PC-3, manufactured by Ishihara
Sangyo Kaisha, Ltd.) as the component (E). These compounds were
mixed in the same order as Example 6 to obtain a composition.
[0136] When an attempt was made to obtain a cured test piece
similarly to Example 5 except that this composition was used, only
a cracked test piece was obtained so that it could not be
evaluated.
Comparative Example 4
[0137] Materials used in respective components were: 25 g of
triethylene glycol dimethacrylate (tradename: NK Ester 3G,
molecular weight: 286, manufactured by Shin-Nakamura Chemical Co.,
Ltd.), which does not correspond to the component (A); 22.5 g of
1-adamantyl methacrylate (tradename: Adamantate M-104, manufactured
by Idemitsu Kosan Co., Ltd.) as the component (B); 2.5 g of
glycidyl methacrylate (manufactured by Wako Pure Chemical
Industries, Ltd.) as the component (C); 0.5 g of
1,1-bis(t-hexylperoxy)cyclohexane (tradename: Perhexa HC,
manufactured by NOF Corp.) as the component (D), and 0.25 g of
Sumilizer GA-80 (tradename, manufactured by Sumitomo Chemical Co.,
Ltd.) and 0.25 g of Sumilizer TP-D (tradename, manufactured by
Sumitomo Chemical Co., Ltd.) as the antioxidants; and 5 g of
titanium dioxide (tradename: Tipaque PC-3, manufactured by Ishihara
Sangyo Kaisha, Ltd.) as the component (E). These compounds were
mixed in the same order as Example 5 to obtain a composition.
[0138] When an attempt was made to obtain a cured test piece
similarly to Example 5 except that this composition was used, only
a cracked test piece was obtained so that it could not be
evaluated.
TABLE-US-00002 TABLE 2 Compar- Compar- Compar- ative ative ative
Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 5 ple 6
ple 7 ple 8 ple 9 ple 10 ple 2 ple 3 ple 4 Compo- Dual-end reactive
silicone oil (g) -- -- -- -- -- 25 White -- -- nent (A) (% by mass)
*1 -- -- -- -- -- 50% Poly- -- -- Lauryl acrylate (g) 15 -- -- --
15 -- phthalamide -- -- (% by mass) *1 30% -- -- -- 30% -- resin --
-- Polyethylene glycol #400 5 -- -- -- -- -- -- -- dimethacrylate
(g) (% by mass) *1 10% -- -- -- -- -- -- -- Hydrogenated
polybutadiene diacrylate (g) -- 25 -- -- -- -- -- -- (% by mass) *1
-- 50% -- -- -- -- -- -- Hydrogenated polyisoprene diacrylate (g)
-- -- 25 25 -- -- 2.5 -- (% by mass) *1 -- -- 50% 50% -- -- 5% --
Ethoxylated (9) trimethylolpropane -- -- -- -- 10 -- -- --
triacrylate (g) (% by mass) *1 -- -- -- -- 20% -- -- -- Triethylene
glycol dimethacrylate (g) 25 (% by mass) *1 50% Compo- 1-Adamantyl
methacrylate (g) 25 22.5 22.5 22.5 22.5 22.5 46.5 22.5 nent (B) (%
by mass) *1 50% 45% 45% 45% 45% 45% 93% 45% Compo- Glycidyl
methacrylate (g) 5 2.5 2.5 2.5 2.5 2.5 1 2.5 nent (C) (% by mass)
*1 10% 5% 5% 5% 5% 5% 2% 5% Compo-
1,1-Bis(t-hexylperoxy)cyclohexane (g) 0.5 1 1 1 0.5 0.5 1 0.5 nent
(D) (parts by mass)*2 1 2 2 2 1 1 2 1 Anti- IRGANOX 3114 (g) 0.25
-- -- -- -- -- -- -- oxidant Sumilizer GA-80 (g) -- 0.25 0.25 0.25
0.25 0.25 0.25 0.25 Sumilizer TP-D (g) -- 0.25 0.25 0.25 0.25 0.25
0.25 0.25 Compo- Titanium dioxide (g) 75 35 5 12.5 50 5 5 5 nent
(E) (parts by mass)*2 150 70 10 25 100 10 10 10 Photo-reflectance
(%) Initial 98 98 98 99 99 98 90 Unevalu- Unevalu- (450 nm) After
168 hours -- -- -- -- -- -- 57 able able at 150.degree. C. After
1000 hours 93 95 94 96 96 95 -- at 150.degree. C. Heat resistance
and light resistance Good Good Good Good Good Good Poor IRGANOX
3114: trade name, manufactured by BASF SE Sumilizer GA-80: trade
name, manufactured by Sumitomo Chemical Co., Ltd. Sumilizer TP-D:
trade name, manufactured by Sumitomo Chemical Co., Ltd. *1: % by
mass based on totality of the components (A), (B) and (C) *2parts
by mass relative to 100 parts by mass of totality of the components
(A), (B) and (C)
[0139] As can be seen in Table 2, in Comparative Example 2 in which
white polyphthalamide resin was used, initial value of the
photo-reflectance was 90%, which was decreased to 57% after 168
hours at 150.degree. C. In addition, color of the irradiated
surface was changed to brown after the LED burn-in test. In
Comparative Example 3 in which content of the component (A) was too
small and in Comparative Example 4 in which polyalkylene glycol
(meth)acrylate having number-average molecular weight of not more
than 400, which does not correspond to the component (A), was used,
flexibility could not be obtained because contribution of the
component (A) was too small. On the contrary, in Examples 5 to 10
in which compositions of the present invention were used, not only
the initial values of photo-reflectance (98 to 99%), but also the
values even after 1,000 hours at 150.degree. C. were high (93 to
96%). In addition, there was no color change after the LED burn-in
test. Accordingly, it was concluded that the composition of the
present invention can provide a cured product having high
reflectance in the visible light region without decrease of the
reflectance even after a long-term usage, and having the excellent
heat resistance and light resistance with less yellowing.
INDUSTRIAL APPLICABILITY
[0140] The (meth)acrylate composition of the present invention can
provide a cured product having high reflectance in the visible
light region with the excellent whiteness, heat resistance, and
light resistance, and with less yellowing, and in addition, having
the excellent adhesion with adjacent parts (especially with the
lead frame); and thus, the composition can be used suitably as a
raw material of a reflective material for an optical
semiconductor.
[0141] The reflective material made using the cured product
obtained by curing the (meth)acrylate composition of the present
invention does not decrease in its reflectance even after a
long-term usage, while having high reflectance in the visible light
region and the excellent adhesion with adjacent parts. The
reflective material of the present invention may be used for a lamp
reflector of a liquid crystal display, a reflective board of a
showcase, a reflective board of various illumination apparatuses, a
reflective material for LED, and so on. Specific examples of a
photoelectric conversion element containing the reflective material
of the present invention and a photoelectric conversion device
containing the photoelectric conversion element include various OA
equipment, electric and electronic equipment and parts thereof, and
automobile parts, such as a display, a destination sign board, a
car lamp, a signal light, an emergency light, a cell phone, and a
video camera.
* * * * *