U.S. patent application number 16/498518 was filed with the patent office on 2020-01-30 for low-gloss cured product having excellent stain resistance, and manufacturing method therefor.
The applicant listed for this patent is LG HAUSYS, LTD.. Invention is credited to Tae Yi CHOI, Heon Jo KIM, Min Kyung PARK, Ji Yeon SEO.
Application Number | 20200030845 16/498518 |
Document ID | / |
Family ID | 65527465 |
Filed Date | 2020-01-30 |
United States Patent
Application |
20200030845 |
Kind Code |
A1 |
SEO; Ji Yeon ; et
al. |
January 30, 2020 |
LOW-GLOSS CURED PRODUCT HAVING EXCELLENT STAIN RESISTANCE, AND
MANUFACTURING METHOD THEREFOR
Abstract
The present invention relates to a cured product having
excellent stain resistance and low gloss, a method of manufacturing
the same, and an interior material including the cured product. The
cured product according to the present invention includes, along
with an acrylic oligomer, an oligomer having a functional group
containing silicon (Si) and an oligomer having a functional group
containing fluorine (F), and thus, has excellent stain resistance
and can implement a micro-folded structure on a surface thereof
through extreme ultraviolet rays to be used during curing, thereby
being capable of realizing low gloss without a matting agent.
Inventors: |
SEO; Ji Yeon; (Seoul,
KR) ; KIM; Heon Jo; (Seoul, KR) ; PARK; Min
Kyung; (Seoul, KR) ; CHOI; Tae Yi; (Seoul,
KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
LG HAUSYS, LTD. |
Seoul |
|
KR |
|
|
Family ID: |
65527465 |
Appl. No.: |
16/498518 |
Filed: |
August 21, 2018 |
PCT Filed: |
August 21, 2018 |
PCT NO: |
PCT/KR2018/009554 |
371 Date: |
September 27, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09D 4/00 20130101; B05D
2506/10 20130101; B05D 2518/10 20130101; E04F 15/105 20130101; B05D
5/02 20130101; B05D 2252/04 20130101; C09D 7/61 20180101; B05D 7/04
20130101; C09D 133/06 20130101; C09D 183/10 20130101; B05D 3/06
20130101; B05D 3/02 20130101; B05D 3/067 20130101; C09D 143/04
20130101; B05D 3/10 20130101; C09D 5/28 20130101 |
International
Class: |
B05D 3/02 20060101
B05D003/02; B05D 3/10 20060101 B05D003/10; C09D 133/06 20060101
C09D133/06; C09D 5/28 20060101 C09D005/28; C09D 7/61 20060101
C09D007/61 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 28, 2017 |
KR |
10-2017-0108613 |
Claims
1. A cured product, comprising: a resin composition comprising an
oligomer comprising a silicon (Si)-containing functional group; an
oligomer comprising a fluorine (F)-containing functional group; and
an acrylic oligomer, wherein a surface of the cured product has a
micro-folded structure, and a surface gloss of the cured product is
9 or less under a 60.degree. gloss condition.
2. The cured product according to claim 1, wherein a weight change
in the cured product subjected to a Taber abrasion resistance test
500 times using an H-18 abradant is 400 mg or less.
3. The cured product according to claim 1, wherein the acrylic
oligomer has a weight average molecular weight (Mw) of 100 to
20,000.
4. The cured product according to claim 1, wherein the resin
composition further comprises one or more monomers selected from
the group consisting of hydroxypropylacrylate,
hydroxypropyl(meth)acrylate, 4-hydroxybutyl (meth)acrylate,
6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate,
2-hydroxyethylene glycol (meth)acrylate or 2-hydroxypropylene
glycol (meth)acrylate, acrylic acid, methacrylic acid,
2-(meth)acryloyloxyacetic acid, 3-(meth)acryloyloxypropyl acid,
4-(meth)acryloyloxybutyl acid, 1,6-hexanediol diacrylate, an
acrylic acid duplex, itaconic acid, maleic acid,
caprolactone-modified hydroxyl acrylate (CHA), tetraethylene glycol
diacrylate, tripropylene glycol diacrylate, dipropylene glycol
diacrylate, triethylene glycol diacrylate, pentaerythritol
triacrylate, and trimethylolpropane ethoxy triacrylate.
5. The cured product according to claim 4, wherein the resin
composition comprises: 100 parts by weight of the acrylic oligomer;
10 to 40 parts by weight of the oligomer comprising a silicon
(Si)-containing functional group; 5 to 15 parts by weight of the
oligomer comprising a fluorine (F)-containing functional group; and
30 to 150 parts by weight of the monomer.
6. The cured product according to claim 1, wherein the resin
composition further comprises inorganic particles having an average
diameter of 1 nm to 100 nm.
7. The cured product according to claim 6, wherein the content of
the inorganic particles is 1 to 40 parts by weight based on 100
parts by weight of the total resin composition.
8. A method of manufacturing a cured product, the method
comprising: a first light irradiation step of irradiating a resin
composition comprising an oligomer comprising a silicon
(Si)-containing functional group; an oligomer comprising a fluorine
(F)-containing functional group; and an acrylic oligomer with light
having a wavelength of 300 nm or less to activate a resin
composition; a second light irradiation step of irradiating the
activated resin composition with light having a wavelength of 700
nm or higher to thermally cure the resin composition; and a third
light irradiation step of irradiating the thermally cured resin
composition with light having a wavelength of 400 nm or less to
optically cure the resin composition.
9. The method according to claim 8, wherein the first and third
light irradiation steps are performed under an inert gas condition
where the concentration of oxygen (O.sub.2) is 10 ppm to 10,000
ppm.
10. The method according to claim 8, wherein, in the second light
irradiation step, a surface temperature of the resin composition is
20 to 90.degree. C.
11. The method according to claim 8, wherein the resin composition
has a viscosity of 100 cps to 1,000 cps at 25.+-.1.degree. C.
12. The method according to claim 8, further comprising, after the
third light irradiation step, a fourth light irradiation step of
irradiating the optically cured resin composition with light having
a wavelength of 700 nm or higher to thermally cure the resin
composition.
13. An interior material, comprising a substrate; and the cured
product according to claim 1 formed on the substrate.
14. The interior material according to claim 13, wherein the
interior material is a flooring material.
Description
TECHNICAL FIELD
[0001] The present invention relates to a cured product having
excellent stain resistance and low gloss, a method of manufacturing
the same, and an interior material including the cured product, and
more particularly, to a cured product having excellent stain
resistance due to the inclusion of a predetermined amount of an
oligomer having a functional group containing silicon (Si) and/or
fluorine (F), and having a folded structure on a surface thereof
through irradiation of a resin composition with extreme ultraviolet
rays during a manufacturing process and thus exhibiting low gloss
without use of a matting agent; and an interior material including
the cured product.
BACKGROUND ART
[0002] In general, residential flooring, which is generally used to
finish floors of living rooms and rooms of detached houses or
apartments, provides a hygienic space by blocking dust and chilly
air from a cement floor. Such residential flooring is printed with
various beautiful patterns, thereby providing decorative effects
such as changing an indoor atmosphere to make it cozy according to
customer demand When a surface of such existing flooring is
contaminated with contaminants, a user cannot easily remove traces
of the contaminants. Such flooring with traces of contaminants
cannot fulfill basic functions thereof.
[0003] To address such a problem, a surface treatment layer is
formed on an uppermost layer of a flooring material, whereby stain
resistance, as well as abrasion resistance and scratch resistance,
are imparted to the flooring material. However, in the case of
conventional flooring, stain resistance is decreased as gloss
decreases, whereby difficulty in cleaning greatly increases.
Accordingly, it is difficult to impart natural gloss, as in a
natural material, while maintaining high stain resistance. In
particular, when conventional flooring materials, to which stain
resistance is imparted, are contaminated by oil-based magic-marker
marks and other pollutants, the contaminants are erased from a
flooring material having a gloss of 10 or higher, but are not
erased from a flooring material having a gloss of 8 or less, based
on a 60 degree gloss meter. In addition, stain resistance is
rapidly decreased due to abrasion of silicon included in an
ultraviolet-cured surface treatment composition for treating
surfaces of the flooring materials. In addition, a conventional
ultraviolet-cured surface treatment composition includes a
considerable amount of micrometer (.mu.m)-sized silica as a matting
agent so as to lower the gloss of a flooring material treated
therewith. Since such silica is porous and has a very low apparent
specific gravity, fine dust, moisture, oil, and the like are easily
adsorbed and stain resistance is rapidly decreased, as a use amount
of the silica increases. In addition, traces such as fingerprints,
footprints, and sweat stains remain on a surface of a floor
material surface-treated with the matting agent, and the appearance
of the floor material becomes cloudy like fog.
[0004] Accordingly, there is an urgent need for development of a
material having improved stain resistance to the extent of
preventing easy contamination by oil stains, food stains, pencil
marks, dust, and ingrained stains at home, while realizing the
gloss of a flooring material in a low state without a matting agent
such as micrometer (.mu.m)-sized silica.
DISCLOSURE
Technical Problem
[0005] The present invention is directed to providing a cured
product exhibiting excellent stain resistance while realizing
surface gloss in a low state without use of a matting agent, and an
interior material using the cured product.
Technical Solution
[0006] One aspect of the present invention provides a cured
product, including:
[0007] a resin composition including an oligomer including a
silicon (Si)-containing functional group; an oligomer including a
fluorine (F)-containing functional group; an acrylic oligomer; a
monomer; and an initiator,
[0008] wherein a surface of the cured product has a micro-folded
structure, and
[0009] a surface gloss of the cured product is 9 or less under a
60.degree. gloss condition.
[0010] Another aspect of the present invention provides a method of
manufacturing a cured product, the method including:
[0011] a first light irradiation step of irradiating a resin
composition including an oligomer including a silicon
(Si)-containing functional group; an oligomer including a fluorine
(F)-containing functional group; and an acrylic oligomer with light
having a wavelength of 300 nm or less to activate a resin
composition;
[0012] a second light irradiation step of irradiating the activated
resin composition with light having a wavelength of 700 nm or
higher to thermally cure the resin composition; and
[0013] a third light irradiation step of irradiating the thermally
cured resin composition with light having a wavelength of 400 nm or
less to optically cure the resin composition.
[0014] Still another aspect of the present invention provides an
interior material including a substrate and the cured product
formed on the substrate.
Advantageous Effects
[0015] A cured product according to the present invention includes,
along with an acrylic oligomer, an oligomer having a functional
group containing silicon (Si) and an oligomer having a functional
group containing fluorine (F), and thus, the cured product has
excellent stain resistance and a micro-folded structure can be
realized on a surface of the cured product through extreme
ultraviolet rays to be used during curing, whereby low gloss can be
realized without a matting agent.
DESCRIPTION OF DRAWINGS
[0016] FIG. 1 is a structural diagram briefly illustrating the
structure of a light-curing apparatus used in the present
invention.
[0017] FIG. 2 is an electron microscope image illustrating a
micro-folded shape of a surface of a cured product according to the
present invention.
BEST MODE FOR CARRYING OUT THE INVENTION
[0018] As the invention allows for various changes and numerous
embodiments, particular embodiments are illustrated in the drawings
and described in detail in the written description.
[0019] However, this is not intended to limit the present invention
to particular modes of practice, and it is to be appreciated that
all changes, equivalents, and substitutes that do not depart from
the spirit and technical scope of the present invention are
encompassed in the present invention.
[0020] In the present invention, the terms such as "include" or
"comprise" should be construed to denote a certain characteristic,
number, step, operation, constituent element, or a combination
thereof, but should not be construed to exclude the existence of or
a possibility of addition of one or more other characteristics,
numbers, steps, operations, constituent elements, or combinations
thereof.
[0021] The present invention relates to an extreme
ultraviolet-cured product and an interior material including the
same.
[0022] When a surface of existing flooring is contaminated with
contaminants, a user cannot easily remove traces of the
contaminants. Such flooring with traces of contaminants cannot
fulfill basic functions thereof. To address such a problem, a
surface treatment layer is formed on an uppermost layer of a
flooring material, whereby stain resistance, as well as abrasion
resistance and scratch resistance, are imparted to the flooring
material.
[0023] However, in the case of conventional flooring, stain
resistance is decreased as gloss is low, whereby difficulty in
cleaning greatly increases. Accordingly, it is difficult to impart
natural gloss, as in a natural material, while maintaining high
stain resistance. In particular, when conventional flooring
materials, to which stain resistance is imparted, are contaminated
by oil-based magic-marker marks and other pollutants, the
contaminants are erased from a flooring material having a gloss of
10 or higher, but are not erased from a flooring material having a
gloss of 8 or less, based on a 60 degree gloss meter. In addition,
stain resistance is rapidly decreased due to abrasion of silicon
included in an ultraviolet-cured surface treatment composition for
treating surfaces of the flooring materials. In addition, a
conventional ultraviolet-cured surface treatment composition
includes a considerable amount of micrometer (.mu.m)-sized silica
as a matting agent so as to lower the gloss of a flooring material
treated therewith. Since such silica is porous and has a very low
apparent specific gravity, fine dust, moisture, oil, and the like
are easily adsorbed and stain resistance is rapidly decreased, as
the content of the silica increases. In addition, traces such as
fingerprints, footprints, and sweat stains remain on a surface of a
floor material surface-treated with the matting agent, and the
appearance of the floor material becomes cloudy like fog.
[0024] Accordingly, the present invention provides a cured product
having excellent stain resistance and low gloss.
[0025] A cured product according to the present invention includes,
along with an acrylic oligomer, an oligomer having a functional
group containing silicon (Si) and an oligomer having a functional
group containing fluorine (F), and thus, the cured product has
excellent stain resistance and a micro-folded structure can be
realized on a surface of the cured product through extreme
ultraviolet rays to be used during curing, whereby low gloss can be
realized without a matting agent.
[0026] Hereinafter, the present invention is described in more
detail.
Cured Product
[0027] An embodiment of the present invention provides
[0028] a cured product of a resin composition including an oligomer
including a silicon (Si)-containing functional group; an oligomer
including a fluorine (F)-containing functional group; and an
acrylic oligomer,
[0029] wherein a surface of the cured product has a micro-folded
structure, and
[0030] the cured product has a surface gloss of 9 or less under a
60.degree. gloss condition.
[0031] The cured product according to the present invention is
manufactured by curing a resin composition, has excellent stain
resistance, and has low gloss, without the inclusion of a matting
agent, due to a micro-folded structure formed on a surface thereof.
In particular, the cured product may be cured by irradiating a
resin composition with extreme ultraviolet rays of less than 300
nm, thereby realizing a micro-folded structure on a surface
thereof. The formed micro-folded structure may induce scattering of
light incident on a surface of the cured product, thereby reducing
gloss.
[0032] As one example, a reduced surface gloss of the cured product
according to the present invention may be 9 or less under a
60.degree. gloss condition using a gloss meter. In particular, an
upper limit of the reduced surface gloss may be 8 or less, 7.5 or
less, 7 or less, 6.5 or less, 6 or less, or 5 or less, and a lower
limit thereof may be 0.1 or more, 0.5 or more, 1 or more, 1.5 or
more, 2 or more, 2.5 or more, or 3 or more. For example, a surface
gloss of the cured product may be 1 to 8, 1 to 7, 1 to 6, 4 to 8, 4
to 7, 7 to 9, 7.2 to 8.7, 4 to 6, 2 to 5, 2.5 to 3.5, 4.5 to 5.5,
2.8 to 5.2, or 3.2 to 4.7.
[0033] In addition, the resin composition used to manufacture the
cured product includes an oligomer including a silicon
(Si)-containing functional group and an oligomer including a
fluorine (F)-containing functional group, thereby having excellent
stain resistance. In particular, the oligomer including a silicon
(Si)-containing functional group and/or a fluorine (F)-containing
functional group included in the resin composition serves to
increase surface tension of the resin composition. The surface
tension-increased resin composition may form a cured product having
low surface energy upon curing. Accordingly, the cured product
having low surface energy has excellent stain resistance, whereby
adsorption of fine dust, moisture, oil, and the like thereto is
prevented.
[0034] For example, since a surface of the cured product according
to the present invention has improved stain resistance, a surface
area of the cured product surface contaminated by oily magic-marker
marks may be 5% or less, particularly 4% or less, 3% or less, 2% or
less, based on an initial contamination area, when removed with dry
cotton fiber, generally used at home, 30 seconds after the
contamination. In some cases, the oily magic marker ingredient on
the surface may be completely removed to the extent of not being
visually observed.
[0035] Here, the oligomer including a silicon (Si)-containing
functional group and/or a fluorine (F)-containing functional group
included in the resin composition may be a silicon-modified acrylic
resin or a fluorine-containing acrylic resin. For example, the
silicon-modified acrylic resin may be an oligomer prepared by
polymerizing an acrylic monomer, such as alkylacrylate or
alkyl(meth)acrylate, with an alkoxysilane-based acrylic monomer
such as 3-methacryloxypropyltrimethoxysilane (MPTS) having a
silicon (Si)-containing functional group, or a silicon urethane
acrylate polymer or silicon polyester acrylate polymer prepared by
modifying a urethane acrylate polymer or polyester acrylate with
silicon (Si). In addition, the fluorine-containing acrylic resin
may be obtained by polymerizing fluorine-containing alkyl acrylate
or fluorine-containing alkyl(meth)acrylate, but the present
invention is not limited thereto.
[0036] In addition, the resin composition includes an oligomer
including a silicon (Si)-containing functional group and/or a
fluorine (F)-containing functional group, and an acrylic oligomer
and monomer used as bases.
[0037] In particular, the resin composition may include 100 parts
by weight of an acrylic oligomer; 10 to 40 parts by weight of an
oligomer including a silicon (Si)-containing functional group; 5 to
15 parts by weight of an oligomer including a fluorine
(F)-containing functional group; and 40 to 150 parts by weight of a
monomer.
[0038] As one example, the resin composition may include, based on
100 parts by weight of the acrylic oligomer, 15 to 40 parts by
weight, 15 to 30 parts by weight, 18 to 35 parts by weight, 18 to
25 parts by weight, 20 to 30 parts by weight, 20 to 40 parts by
weight, 25 to 40 parts by weight, 25 to 30 parts by weight, 18 to
22 parts by weight, or 22 to 27 parts by weight of the oligomer
including a silicon (Si)-containing functional group; 5 to 13 parts
by weight, 8 to 13 parts by weight, 5 to 10 parts by weight, 8 to
10 parts by weight, 10 to 15 parts by weight, 12 to 15 parts by
weight, or 11 to 13 parts by weight of the oligomer including a
fluorine (F)-containing functional group; and 30 to 130 parts by
weight, 30 to 110 parts by weight, 30 to 90 parts by weight, 30 to
70 parts by weight, 30 to 60 parts by weight, 50 to 150 parts by
weight, 70 to 150 parts by weight, 90 to 150 parts by weight, 110
to 150 parts by weight, 130 to 150 parts by weight, 80 to 130 parts
by weight, 90 to 125 parts by weight, 110 to 125 parts by weight,
118 to 122 parts by weight, 50 to 90 parts by weight, 50 to 75
parts by weight, 50 to 65 parts by weight, 55 to 65 parts by
weight, 57 to 62 parts by weight, 48 to 52 parts by weight, 45 to
55 parts by weight, 55 to 65 parts by weight, 115 to 125 parts by
weight, or 35 to 55 parts by weight of the monomer.
[0039] As one example, the resin composition may include 100 parts
by weight of the acrylic oligomer; 23 to 28 parts by weight of the
oligomer including a silicon (Si)-containing functional group; 9 to
12 parts by weight of the oligomer including a fluorine
(F)-containing functional group; and 48 to 52 parts by weight of
the monomer.
[0040] In addition, the acrylic oligomer is not specifically
limited so long as it is obtained using a monomer including an
acryl group. For example, the acrylic oligomer may include a
(meth)acrylate oligomer, a urethane (meth)acrylate oligomer,
etc.
[0041] In addition, the acrylic oligomer may have a weight average
molecular weight (Mw) of 100 to 20,000, more particularly a weight
average molecular weight (Mw) of 100 to 10,000, 100 to 5,000, 500
to 3,000, 500 to 2,500, 500 to 2000, 900 to 1,100, 1,000 to 3,000,
1,000 to 2,500, 2,200 to 2,600, 4,000 to 7,000, 1,000 to 15,000,
1,000 to 11,500, 5,000 to 15,000, 8,000 to 13,000, 10,000 to
12,000, or 10,000 to 10,000. In the present invention, a weight
average molecular weight (Mw) of the acrylic oligomer is adjusted
within the ranges, whereby durability of the cured product is
further improved.
[0042] In addition, the monomer may be an acrylic monomer,
particularly an acrylate-based monomer containing a hydrophilic
group, but the present invention is not limited thereto. For
example, as the monomer, one or more selected from the group
consisting of (meth)acrylate, 2-hydroxyethyl (meth)acrylate,
2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate,
6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate,
2-hydroxyethylene glycol (meth)acrylate or 2-hydroxypropylene
glycol (meth)acrylate, acrylic acid, methacrylic acid,
2-(meth)acryloyloxyacetic acid, 3-(meth)acryloyloxypropyl acid,
4-(meth)acryloyloxybutyl acid, 1,6-hexanediol diacrylate, an
acrylic acid duplex, itaconic acid, maleic acid,
caprolactone-modified hydroxyl acrylate (CHA), tetraethylene glycol
diacrylate, tripropylene glycol diacrylate, dipropylene glycol
diacrylate, triethylene glycol diacrylate, pentaerythritol
triacrylate, and trimethylolpropane ethoxy triacrylate may be
included.
[0043] Further, the resin composition may further include additives
such as a dispersing agent, a leveling agent, a defoaming agent, an
antifoaming agent, a precipitation inhibitor, and a wetting agent.
As one example, to improve abrasion resistance of the cured
product, inorganic particles having high hardness may be further
included. Such inorganic particles are not specifically limited so
long as surface hardness can be increased without affecting the
gloss of a cured product after curing of a resin composition.
Particularly, colloidal silica, alumina, glass beads, organic beads
(polymer particles, etc.), etc., preferably colloidal silica, may
be used.
[0044] In addition, the inorganic particles may have an average
diameter of 1 nm to 100 nm, particularly an average diameter of 10
nm to 100 nm, 10 nm to 80 nm, 10 nm to 60 nm, 10 nm to 40 nm, 10 nm
to 30 nm, or 15 nm to 25 nm. In addition, the content of the
inorganic particles may be 1 part by weight to 40 parts by weight,
particularly 5 to 35 parts by weight, 5 parts by weight to 30 parts
by weight, 5 parts by weight to 25 parts by weight, 10 parts by
weight to 25 parts by weight, 10 parts by weight to 30 parts by
weight, 15 to 25 parts by weight, or 18 to 22 parts by weight,
based on 100 parts by weight of the total resin composition. When
the average diameter and content of the inorganic particles of the
present invention are controlled within the ranges, crack
occurrence in the cured product may be prevented without affecting
the gloss of the cured product, the adhesive strength between the
cured product and other layers may be increased, thereby increasing
durability, and abrasion resistance of the cured product may be
effectively improved.
[0045] As one example, when the cured product according to the
present invention is subjected to an abrasion resistance test 500
times under conditions of an H-18 abradant and a load of 500 g, a
weight change in the worn specimen (width.times.length: 10
cm.times.10 cm, an average thickness of the cured product: 18.+-.2
.mu.m) may be 400 mg or less, particularly 300 to 400 mg, 350 to
400 mg, 370 to 400 mg, 380 to 390 mg, or 383 to 387 mg.
[0046] Method of Manufacturing Cured Product
[0047] In addition, an embodiment of the present invention provides
a method of manufacturing a cured product, the method
including:
[0048] a first light irradiation step of irradiating a resin
composition including an oligomer including a silicon
(Si)-containing functional group; an oligomer including a fluorine
(F)-containing functional group; and an acrylic oligomer with light
having a wavelength of 300 nm or less to activate a resin
composition;
[0049] a second light irradiation step of irradiating the activated
resin composition with light having a wavelength of 700 nm or
higher to thermally cure the resin composition; and
[0050] a third light irradiation step of irradiating the thermally
cured resin composition with light having a wavelength of 400 nm or
less to optically cure the resin composition.
[0051] The present invention includes the steps of sequentially
irradiating the resin composition including an oligomer including a
silicon (Si)-containing functional group; an oligomer including a
fluorine (F)-containing functional group; and an acrylic oligomer
with light in specific different wavelength ranges three times to
cure the resin composition, so that a micro-folded structure may be
realized on a surface of the produced cured product.
[0052] Here, the first light irradiation step is a first step of
irradiating a resin composition applied on a substrate with light.
In the first light irradiation step, an excimer generated by
irradiated light forms wrinkles by shrinking the applied resin
composition and/or a surface of the cured product, thereby
increasing a scattering rate of light incident on the surface. The
present invention includes the first light irradiation step of
forming an excimer, thereby being capable of shrinking the resin
composition and/or a surface of the cured product and increasing a
scattering rate of light. Accordingly, the present invention may
lower a gloss degree of the cured product without use of a matting
agent. For this, the first light irradiation step may be performed
using high-energy light in a wavelength region of 300 nm or less,
particularly 200 nm or less, more particularly 100 to 200 nm, 150
to 190 nm or 160 to 180nm, in a nitrogen (N.sub.2) atmosphere
including a small amount of oxygen (O.sub.2). Here, the
concentration of oxygen (O.sub.2) included in a nitrogen (N.sub.2)
atmosphere may be 10 to 10,000 ppm, particularly 10 to 9,000 ppm,
10 to 7,000 ppm, 10 to 5,000 ppm, 10 to 3,000 ppm, 10 to 1,000 ppm,
10 to 500 ppm, 100 to 300 ppm, 10 to 200 ppm, 5,000 to 9,000 ppm,
4,000 to 6,000 ppm, 1,000 to 5,000 ppm, 1,000 to 2,000 ppm, 2,000
to 3,000 ppm, 3,000 to 4,000 ppm, 4,000 to 5,000 ppm, 10 to 2,000
ppm, 50 to 500 ppm, 50 to 300 ppm, 50 to 150 ppm, or 80 to 120
ppm.
[0053] As one example, in the first light irradiation step, the
resin composition may be irradiated with light having a wavelength
of 175.+-.2 nm for a very short time of 1 to 2 seconds under a
nitrogen (N.sub.2) condition containing 100.+-.10 ppm of oxygen
(O.sub.2) so as to form an excimer in the resin composition.
[0054] In addition, the resin composition may be applied to the
substrate by a method known in the technical field to which the
present invention pertains. For example, methods such as rubber
rolling, G/V rolling, an air knife method, and a slot die method
may be used.
[0055] In addition, the second light irradiation step is a step of
applying thermal energy to the surface-shrunk resin composition
and/or cured product to activate the same. Here, the thermal energy
may be applied by irradiating a wavelength of 700 nm or more,
particularly a wavelength of 700 nm to 900 nm, 750 nm to 900 nm, or
750 nm to 850 nm, under an air condition. The temperature of a
thermal energy-applied resin composition and/or cured product
surface may be 20.degree. C. to 90.degree. C., particularly
30.degree. C. to 80.degree. C.
[0056] As one example, the second light irradiation step may be
performed by irradiating the resin composition and/or the cured
product with light having a wavelength of 800.+-.2 nm for a very
short time of 1 to 2 seconds under an air condition.
[0057] In addition, the third light irradiation step is a step of
primarily applying light energy to the thermally cured resin
composition and/or a cured product to cure the same. Here, the
light energy may be applied using light having a wavelength of 400
nm or less, particularly a wavelength of 100 nm to 400 nm, 200 nm
to 400 nm, 200 nm to 300 nm, 300 nm to 400 nm, 150 nm to 300 nm,
200 nm to 250 nm, or 270 nm to 320 nm, in a nitrogen (N.sub.2)
atmosphere including a small amount of oxygen (O.sub.2). Here, the
concentration of oxygen (O.sub.2) included in the nitrogen
(N.sub.2) atmosphere may be 10 to 10,000 ppm, particularly 10 to
9,000 ppm, 10 to 7,000 ppm, 10 to 5,000 ppm, 10 to 3,000 ppm, 10 to
1,000 ppm, 10 to 500 ppm, 100 to 300 ppm, 10 to 200 ppm, 5,000 to
9,000 ppm, 4,000 to 6,000 ppm, 1,000 to 5,000 ppm, 1,000 to 2,000
ppm, 2,000 to 3,000 ppm, 3,000 to 4,000 ppm, 4,000 to 5,000 ppm, 10
to 2,000 ppm, 50 to 500 ppm, 50 to 300 ppm, 50 to 150 ppm, or 80 to
120 ppm.
[0058] Further, the method of manufacturing the cured product
according to the present invention may further include, after the
third light irradiation step, a fourth light irradiation step of
irradiating the optically cured resin composition with light having
a wavelength of 700 nm or higher to thermally cure the resin
composition. The fourth light irradiation step is a step of
additionally performing thermal curing of the resin composition.
Here, the thermal energy may be applied by irradiating light having
a wavelength of 700 nm or more, particularly a wavelength of 700 nm
to 900 nm, 750 nm to 900 nm, or 750 nm to 850 nm, under an air
condition. The temperature of the thermal energy-applied resin
composition and/or cured product surface may be 20 to 90.degree.
C., particularly 30.degree. C. to 80.degree. C.
[0059] As one example, the fourth light irradiation step may be
performed by irradiating the resin composition and/or the cured
product with light having a wavelength of 800.+-.2 nm for a very
short time of 1 to 2 seconds under an air condition.
[0060] In the present invention, light having a wavelength required
in each step may be irradiated according to known methods. For
example, light having a wavelength of 400 nm or less, which is in a
UV region, may be irradiated using a mercury or metal halide lamp,
or the like. Here, a light irradiation amount may be 500
mJ/cm.sup.2 to 1,300 mJ/cm.sup.2, or 700 mJ/cm.sup.2 to 1,100
mJ/cm.sup.2.
[0061] In addition, in the present invention, a light irradiation
time may be a very short time of 1 to 2 seconds. Such a light
irradiation time may be controlled according to a migration rate of
a resin composition, e.g., a migration rate of a resin composition
coated on a substrate, during light irradiation. For example, a
migration rate of the resin composition and/or the substrate coated
with the resin composition may be 1 to 50 m/min, particularly 5 to
40 m/min, 10 to 40 m/min, 20 to 40 m/min, 30 to 40 m/min, 15 to 25
m/min, 5 to 15 m/min, 15 to 20 m/min, 35 to 40 m/min, or 18 to 22
m/min.
[0062] Meanwhile, the resin composition used in the present
invention excludes a matting agent for reducing the gloss of a
cured product, unlike existing resin compositions. Accordingly, the
resin composition may have a viscosity of 100 cps to 1,000 cps,
particularly 800 cps or less, at 25.degree. C. More particularly,
the resin composition may have a low viscosity of 600 cps or less,
100 to 500 cps, 100 to 450 cps, 150 to 350 cps, 200 to 350 cps, 250
to 350 cps, 280 to 300 cps, 400 to 500 cps, or 440 to 460 cps. Even
when inorganic particles are further included to increase the
durability of the cured product, a low viscosity of 500 to 750 cps
may be exhibited. The resin composition has an advantage of
excellent workability by having such a low viscosity.
[0063] Interior material
[0064] Further, an embodiment of the present invention provides an
interior material including the cured product according to the
present invention.
[0065] The interior material according to the present invention
includes the aforementioned cured product according to the present
invention, thereby simultaneously realizing low gloss and high
stain resistance and abrasion resistance. Accordingly, the interior
material may be usefully used for flooring requiring low gloss and
high durability, and the like.
[0066] Here, the interior material may include the cured product
according to the present invention as a surface treatment layer
formed on a substrate thereof. As needed, so as to add functions to
the interior material, functional layers such as a printed layer, a
balance layer, and a dimensionally stable layer may be further
included between the substrate and the cured product as a surface
treatment layer. As one example, the interior material may have a
structure wherein a balance layer, a substrate layer, a printed
layer, a transparent layer, and a surface treatment layer are
sequentially laminated, or a structure wherein a substrate layer, a
printed layer, a transparent layer, and a surface treatment layer
are sequentially laminated.
[0067] Here, the transparent layer, the printed layer, the
substrate layer, and the balance layer, for example, may be formed
by optically or thermally curing respective compositions including
at least one selected from the group consisting of a binder resin,
an initiator, a curing agent, other additives, and a combination
thereof, or may be formed in a film or sheet shape using an
extrusion method, a calendering method, or the like.
[0068] In addition, the types and contents of components included
in each of the compositions may be appropriately adjusted, without
specific limitation, according to the property and function of each
layer thereof.
[0069] In particular, the flooring material may be formed by
applying a predetermined composition to one surface of any one
layer thereof, and then optically or thermally curing the same, or
may be manufactured by forming respective layers thereof as a film
or a sheet, and then laminating the same by a lamination process
known in the art, but the present invention is not limited
thereto.
[0070] In addition, the binder resin may include a synthetic resin,
a bioresin, or both, for example, a polyvinyl chloride (PVC) resin,
a polyurethane resin, a polylactic acid-based resin, a polyolefin
resin, or the like, but the present invention is not limited
thereto.
[0071] In addition, the transparent layer may have a thickness of
about 0.05 mm to about 2.0 mm. When the thickness of the
transparent layer is within the range, a design or pattern of a
printed layer laminated under the transparent layer, as described
below, may be sufficiently protected without an excessive increase
in the thickness of the flooring material.
[0072] In addition, a pattern of the printed layer may be formed in
various ways such as, for example, transfer printing, gravure
printing, screen printing, offset printing, rotary printing, and
flexographic printing. Further, the printed layer may have a
thickness of about 1 .mu.m to about 10 .mu.m, but the present
invention is not limited thereto.
[0073] In addition, the substrate layer is a base layer of the
flooring material and may serve to support a transparent layer and
printed layer formed thereon and absorb impact applied from above
or below. Such a substrate layer is not specifically limited so
long as it is used as a matrix for flooring materials in the art,
and may be, for example, a sheet or film including polyvinyl
chloride (PVC), a polyolefin, polyester such as polyethylene
terephthalate (PET) or glycol-modified polyethylene terephthalate
(PETG), or the like. In addition, the substrate layer may have a
thickness of about 1.0 mm to about 3 0 mm, but the present
invention is not limited thereto.
[0074] Further, the balance layer is a part bonded to a bottom
surface upon construction and may serve to protect a back surface
opposite to a surface of the flooring material and protect against
moisture of the bottom. In addition, the balance layer may have a
thickness of about 1.0 mm to about 3.0 mm, but the present
invention is not limited thereto.
[0075] In addition, one or more of the base layer and the balance
layer may further include at least one selected from the group
consisting of TiO.sub.2, CaCO.sub.3, wood flour, mica, glass fiber,
starch, natural fiber, chaff, rosin, talc, and a combination
thereof.
[0076] In addition, a dimensionally stable layer may be further
included between the printed layer and the base layer. Here, the
dimensionally stable layer may have a thickness of about 0.1 mm to
about 2.0 mm, but the present invention is not limited thereto.
[0077] The dimensionally stable layer may be formed of a composite
material including a binder resin and glass fiber impregnated
therein and serves to reduce a dimensional strain rate even at high
temperature and high humidity. Accordingly, the dimensionally
stable layer may maintain high adhesive strength to other layers
laminated thereon and thereunder while imparting excellent
dimensional stability, thereby realizing excellent durability.
MODE FOR CARRYING OUT THE INVENTION
[0078] Hereinafter, the present invention will be described in
detail by explaining examples and experimental examples of the
invention.
[0079] However, these examples and experimental examples are
provided for illustrative purposes only and should not be construed
as limiting the scope and spirit of the present invention.
EXAMPLES 1 TO 4 AND COMPARATIVE EXAMPLES 1 TO 6
[0080] Resin compositions having compositions summarized in Table 1
were prepared. Each of the prepared resin compositions was applied
to a polyvinyl chloride (PVC) substrate having a width and length
of 10 cm.times.10 cm, followed by fixing to a light-curing
apparatus having a structure shown in FIG. 1. Next, light
irradiation was performed stepwise under curing conditions
summarized in Table 2 below, thereby manufacturing a cured product
specimen formed by curing the resin composition on the substrate.
Here, an average thickness of the cured product was 18.+-.2
.mu.m.
TABLE-US-00001 TABLE 1 (Units: g) Composition 1 Composition 2
Composition 3 Composition 4 Composition 5 Oligomer including 10 10
-- -- 10 silicon-containing functional group Oligomer including 4 4
-- 4 -- fluorine-containing functional group Acrylic oligomer I 20
20 20 20 20 Acrylic oligomer II 20 20 20 20 20 Monomer I 15 15 28
15 15 Monomer II 5 5 10 5 5 Monomer III -- -- 10 10 4
Photoinitiator 2 2 2 2 2 Dispersing agent 0.5 0.5 0.5 0.5 0.5
Leveling agent 1 1 1 1 1 Defoaming agent 0.5 0.5 0.5 0.5 0.5
Antifouling agent 2 2 2 2 2 Quencher -- -- 6 -- -- Inorganic
particles -- 20 -- 20 20 Composition 450 cps 740 cps 600 cps 720
cps 750 cps viscosity (25.degree. C.) Oligomer including
silicon-containing functional group: silicon urethane acrylate
polymer (trade name: Miramer SIU24000, Mw: 40,000 .+-. 1,000)
Oligomer including fluorine-containing functional group: silicon
polyester acrylate (trade name: Miramer LR2000, Mw: 2,500 .+-. 100)
Acrylic oligomer I: Polyurethane acrylate (weight average molecular
weight: 1,100 .+-. 50) Acrylic oligomer II: Polyurethane acrylate
(weight average molecular weight: 2,400 .+-. 50) Monomer I: Hydroxy
propyl acrylate Monomer II: 1,6-hexanediol diacrylate Monomer III:
Trimethylol propane triacrylate Inorganic particles: Silica
nanoparticles (average diameter: 20 .+-. 5 nm)
TABLE-US-00002 TABLE 2 Curing Curing Curing Curing Curing condition
1 condition 2 condition 3 condition 4 condition 5 First light
Wavelength 172 .+-. 5 nm 172 .+-. 5 nm -- 172 .+-. 5 nm 180 .+-. 5
nm irradiation range Irradiation 160 mJ/cm.sup.2 120 mJ/cm.sup.2 --
120 mJ/cm.sup.2 120 mJ/cm.sup.2 amount Substrate 20 .+-. 1 m/min 20
.+-. 1 m/min -- 20 .+-. 1 m/min 20 .+-. 1 m/min migration rate Gas
N.sub.2 N.sub.2 -- N.sub.2 N.sub.2 condition condition condition
condition condition (O.sub.2 100 ppm) (O.sub.2 100 ppm) (O.sub.2
100 ppm) (O.sub.2 100 ppm) Second Wavelength 750 nm or 750 nm or
750 nm or -- 750 nm or light range higher higher higher higher
irradiation Irradiation 80 .+-. 1 mJ/cm.sup.2 60 .+-. 1 mJ/cm.sup.2
80 mJ/cm.sup.2 -- 80 mJ/cm.sup.2 amount Substrate 20 .+-. 1 m/min
20 .+-. 1 m/min 20 .+-. 1 m/min -- 20 .+-. 1 m/min migration rate
Gas Under air Under air Under air -- Under air condition condition
condition condition condition Third Wavelength 250~400 nm 250~400
nm 250~400 nm 250~400 nm -- light range irradiation Irradiation 600
mJ/cm.sup.2 800 mJ/cm.sup.2 600 mJ/cm.sup.2 600 mJ/cm.sup.2 --
amount Substrate 20 .+-. 1 m/min 20 .+-. 1 m/min 20 .+-. 1 m/min 20
.+-. 1 m/min -- migration rate Gas N.sub.2 N.sub.2 N.sub.2 N.sub.2
-- condition condition condition condition condition (O.sub.2 200
ppm) (O.sub.2 200 ppm) (O.sub.2 200 ppm) (O.sub.2 200 ppm) Fourth
Wavelength -- 750 nm or -- -- -- light range higher irradiation
Irradiation -- 60 .+-. 1 mJ/cm.sup.2 -- -- -- amount Substrate --
20 .+-. 1 m/min -- -- -- migration rate Gas -- Under air -- -- --
condition condition
TABLE-US-00003 TABLE 3 Composition type Curing condition Example 1
Composition 1 Curing condition 1 Example 2 Composition 1 Curing
condition 2 Example 3 Composition 2 Curing condition 1 Example 4
Composition 2 Curing condition 2 Comparative Example 1 Composition
3 Curing condition 1 Comparative Example 2 Composition 4 Curing
condition 1 Comparative Example 3 Composition 4 Curing condition 2
Comparative Example 4 Composition 1 Curing condition 3 Comparative
Example 5 Composition 1 Curing condition 4 Comparative Example 6
Composition 1 Curing condition 5
EXPERIMENTAL EXAMPLE 1
[0081] To observe a surface shape of the cured product according to
the present invention, the cured product specimen obtained
according to Example 1 was subjected to electron microscope
analysis. A result thereof is illustrated in FIG. 2.
[0082] Examining FIG. 2, it can be confirmed that a surface of the
cured product according to the present invention has a micro-folded
shape. In particular, when a surface of the cured product was
irradiated with extreme ultraviolet rays of less than 300 nm upon
curing of the cured product, such a micro-folded shape was formed
on the surface.
EXPERIMENTAL EXAMPLE 2
[0083] To evaluate properties of the cured product according to the
present invention, gloss degree, stain resistance, Taber abrasion
resistance, and adhesion of the cured products manufactured in
Examples 1 to 4 and Comparative Examples 1 to 6 were measured.
Particular measurement methods are described below. Measurement
results are summarized in Table 4 below:
[0084] A) Gloss Degree Evaluation
[0085] Measured under a 60.degree. gloss condition using a gloss
meter.
[0086] B) Stain Resistance Evaluation
[0087] A specimen surface was contaminated with oily magic-marker
marks, and after 30 seconds, the oily marks were removed with dry
cotton fiber. A remaining contamination area, based on the initial
contamination area, was observed with the naked eye. Results were
classified as follows:
[0088] Excellent: When a remaining contamination area is less than
5% based on an initial contamination area
[0089] Satisfactory: When a remaining contamination area is 5 to
20% based on an initial contamination area
[0090] Poor: When a remaining contamination area is greater than
20% based on an initial contamination area.
[0091] C) Taber Aabrasion Resistance Evaluation
[0092] The weight of a specimen was measured, and the specimen was
subjected to an abrasion resistance test 500 times using an H-18
abradant and Taber abraser (5135 Rotary Platform abraser,
manufactured by Erichsen) under a load of 500 g, followed by
measuring the weight of the worn specimen so as to compare a weight
change in the specimen before and after the test.
[0093] D) Adhesion Evaluation
[0094] A surface of a specimen was cross-cut by 10 rows
horizontally and vertically at 1 mm intervals by means of a knife
according to a cross cut test method, thereby obtaining 100
sections. Next, a tape was firmly attached to the cut specimen
sections, followed by detaching the tape from the specimen. The
number of detached sections among the 100 sections was counted.
TABLE-US-00004 TABLE 4 Stain Taber weight Number of Gloss degree
resistance change detached sections Example 1 3 .+-. 0.5 excellent
385 mg 0 Example 2 5 .+-. 0.5 excellent 385 mg 0 Example 3 3 .+-.
0.5 excellent 310 mg 0 Example 4 5 .+-. 0.5 excellent 310 mg 0
Comparative 7 .+-. 0.5 poor 426 mg 0 Example 1 Comparative 3 .+-.
0.5 poor 350 mg 0 Example 2 Comparative 5 .+-. 0.5 poor 350 mg 0
Example 3 Comparative 36 .+-. 0.5 excellent 340 mg 0 Example 4
Comparative 5 .+-. 0.5 excellent 480 mg 0 Example 5 Comparative 5
.+-. 0.5 excellent 530 mg 0 Example 6
[0095] As shown in Table 4, it can be confirmed that the cured
product according to the present invention cured by sequentially
irradiating light in different specific wavelength ranges exhibits
low gloss, and even if a resin composition thereof excludes a
matting agent, excellent stain resistance and abrasion
resistance.
[0096] In particular, the cured product specimen of Examples 1 to 4
exhibited a gloss degree of 1 to 6 under a 60.degree. gloss
condition, without use of a matting agent, and high stain
resistance against oily magic-marker marks. In addition, the cured
products exhibited a weight change rate of 400 mg or less,
particularly a weight change rate of about 300 to 390 mg when
subjected to Taber abrasion resistance evaluation due to increased
abrasion resistance, and no section was detached from the cured
products when subjected to cross-cut evaluation.
[0097] On the other hand, it was confirmed that the cured product
specimens of Comparative Examples 1 to 3 including a matting agent
exhibited a gloss degree of 8 or less at a 60.degree. gloss
condition, but exhibited low stain resistance against oily
magic-marker marks. In addition, the cured product specimen of
Comparative Example 4 was not subjected to a step of irradiating
with extreme ultraviolet rays having high energy, thereby
exhibiting a remarkably high gloss degree under a 60.degree. gloss
condition. Further, when the cured product specimen of Comparative
Examples 5 and 6 were subjected to Taber abrasion resistance
evaluation, weight change rates therein were about 450 mg or
more.
[0098] From these results, it can be confirmed that the cured
product includes an oligomer having a functional group containing
silicon (Si) and/or fluorine (F) along with an acrylic oligomer,
and thus, exhibits excellent stain resistance and is capable of
realizing a micro-folded structure on a surface thereof due to
extreme ultraviolet rays used for curing, thereby being capable of
realizing low gloss without a matting agent.
DESCRIPTION OF SYMBOLS
[0099] 100: Light-curing apparatus
[0100] 110: Light irradiation room
[0101] 111: First light irradiator (UV irradiator)
[0102] 112: Second light irradiator (IR irradiator)
[0103] 113: Third light irradiator (UV irradiator)
[0104] 120: Irradiated light
[0105] 130: Conveyor belt
[0106] 140: Gas diaphragm
[0107] 150: Specimen
INDUSTRIAL APPLICABILITY
[0108] A cured product according to the present invention includes,
along with an acrylic oligomer, an oligomer having a functional
group containing silicon (Si) and an oligomer having a functional
group containing fluorine (F), and thus, exhibits excellent stain
resistance and is capable of realizing a micro-folded structure on
a surface thereof due to extreme ultraviolet rays used for curing,
thereby being capable of realizing low gloss without a matting
agent.
* * * * *