JPS6374691A - Sublimating dispersion-dye easily dyeable resin composition - Google Patents

Abstract

PURPOSE:To obtain an easily dyeable resin composition developing a color in a high density, by a method wherein a specific surface-active agent and a polyoxyalkylene resin are compounded in specific amounts with a polyester resin and a crosslinker of specific ratios. CONSTITUTION:A title composition is formed by compunding 100 parts by weight of a mixture consisting of 40-95 wt% of a polyester resin and 60-5 wt% of a crosslinker capable of curing by an activation energy ray, 0.01-10 parts by weight of at least one selected from among silicone surface-active agents and fluorine surface-active agents, and 0.1-30 parts by weight of a polyoxyalkylene derivative. With less than 40 wt% of the polyester resin, a high dyeing density cannot be realized under low-energy conditions; with more than 95 wt% of the polyester resin, the decrease of the crosslinker results in the unsatisfactory non-blocking properties to a transfer paper. The silicone surface-active agent or/and the fluorine surface-active agent can prevent the blocking to a color sheet (transfer paper) in a low-energy thermal transferring. Moreover, the compounding of the polyoxyalkylene derivative with the composition allows a high-density dyeing.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a resin composition for thermal transfer printing of textiles, plastic molded products (films, sheets, lenses, etc.). ) The present invention relates to a resin composition that can be used for heat-sensitive transfer, etc.

[Prior Art] Conventionally, as a transfer composition for a sublimation type heat-sensitive transfer method, a sheet-like material obtained by treating acrylic short m miscellaneous with fullylene carbonate and ammonium salt described in JP-A-60-81359 has been used. , a sheet-like material made of short polyester having an acidic group converted to an ammonium salt type described in JP-A No. 60-112494, etc.; , high energy conditions are required to dye deep colors. In addition, methylol melamine resin is a transferable composition for textile processing, and it is a sublimable disperse dye that can be thermally transferred printed, but it requires high energy for dyeing and has drawbacks in color fastness. .

[Problems to be Solved by the Invention] The object of the present invention is to provide a sublimable disperse dye that is cured with active energy rays and has good light resistance, and that can be easily dyed even under low energy conditions and at a high concentration. An object of the present invention is to provide a resin composition that develops color.

As a result of extensive studies, the present inventors have found that a composition comprising a specific ratio of a polyester resin and a crosslinking agent, a specific surfactant, and a specific amount of a polyoxyalkylene resin is capable of sublimation by curing with active energy rays. The present inventors have discovered that the dye can be easily dyed under low energy conditions and dyed with high concentration using a synthetic disperse dye, and have completed the present invention.

[Means for solving the problems] That is, 1 the present invention uses 40 to 95% by weight of polyester resin.
and 100 parts by weight of a mixture consisting of 60 to 5% by weight of a crosslinking agent that can be cured by active energy rays, and 0.01 to 10 parts by weight of at least one selected from silicone surfactants and fluorine surfactants, and This is a resin composition that is easily dyeable with a sublimable disperse dye and contains 0.1 to 30 parts by weight of a polyoxyalkylene derivative.

The present invention will be explained in detail below.

According to the present invention, the polyester resin constituting the composition is well stained by sublimable disperse dyes and has the ability to act as a binder for the composition, and is one of the essential components of the present Hikari II+. .

The polyester resin is a linear thermoplastic polyester resin obtained by the condensation polymerization of a dicarboxylic acid and a diol, or/and a linear thermoplastic polyester resin obtained by the condensation polymerization of an unsaturated polybasic acid having a reactive double bond and a polyhydric alcohol. Among them, a linear thermoplastic polyester resin having a molecular weight of 12,000 to 40,000 obtained by condensation polymerization of two or more dicarboxylic acids and two or more diols, and having a degree of coagulation is preferable. 1% or less polyester resin has solubility in organic solvents and ease of dyeing.
and more preferable in terms of good light resistance.

The blending amount of the polyester resin is 40 to 40% of the total amount of the crosslinking agent.
It is preferable that the amount is 95% by weight; if it is less than 40% by weight, the dyeing density with the sublimable disperse dye will not become deep under low energy conditions, and conversely, if the amount of polyester resin blended exceeds 95% by weight, the amount of crosslinking agent will decrease. , the non-blocking property with the color sheet (transfer paper) coated with the sublimable disperse dye was poor, and the color sheet and the article coated with the sublimable disperse dye dyeable resin composition and cured with active energy rays were not thermally transferred. More preferably, the content is in the range of 55% to 93% by weight, which sometimes causes blocking (staying).

Specific examples of linear thermoplastic polyester resins obtained by condensation polymerization of two or more dicarboxylic acids and two or more diols include polyester resins obtained from teretsutalumi/isophthalic acid/ethylene glycol/neopentyl glycol; Others terephthalic acid/isophthalic acid/ethylene glycol/bisphenol A-ethyleneoxy I' adduct, terephthalic acid/isophthalic acid/ethylene glycol/1,8-hexanediol, terephthal I
v/Isophthalic acid/Sebacic acid/Ethylene glycol/
Neopentyl glycol, terephthalic acid/sebacic acid/
Examples include polyester resins obtained from ethylene glycol/neopentyl glycol, terephthalic acid/isophthalic acid/Adipine M/ethylene glycol/neopentyl glycol, and two or more types can also be used in combination. Note that using esterified dimethyl terephthalate, dimethyl isophthalate, etc. instead of terephthalic acid, isophthalic acid, etc. as a raw material for condensation polymerization is also, of course, a circular method.

Examples of unsaturated polyester resins obtained by condensation polymerization of unsaturated polybasic acids having reactive double bonds and polyhydric alcohols include maleic anhydride/phthalic anhydride/propylene glycol, maleic anhydride/inphthalic anhydride/ From propylene glycol, maleic acid/fumaric acid/inphthalic acid/1,3-butanediol, maleic acid/isophthalic acid/neopentyl glycol, maleic anhydride/tetrahydrophthalic anhydride/dipropylene glycol, etc.
! Examples of resins that can be used include:

The crosslinking agent is necessary to cure the resin composition of the invention with active energy rays and to obtain blocking resistance of the cured resin composition, and the preferred amount is 5 to 60% weight Q of the total amount with the polyester resin. %, more preferably from 7 to 45%. The amount of crosslinking agent is 5ffi amount%
When it is less than 60% by weight, blocking tends to occur, and on the other hand, when it exceeds 60% by weight, although blocking resistance is good, the proportion of the polyester resin decreases, making it difficult to obtain a sufficient dyeing density.

Considering the curing of the composition by the crosslinking agent and the blocking resistance of one composition, it is preferable that the crosslinking agent has at least one kind of polyfunctional polymer, and ultraviolet rays, which are easily handled as active energy rays, are preferably used. When used, the polymerizable group of these crosslinking agents is preferably a hexamer having an acryloyloxy group or a methacryloyloxy group.

Examples of hexamers having a (meth)acryloyloxy group include polyether acrylate or polyether methacrylate (hereinafter, "acrylate or methacrylate" will be abbreviated as "(meth)acrylate"), polyester (meth) Monomers such as acrylate, polyol (meth)acrylate, epoxy (meth)acrylate, amide urethane (meth)acrylate, urethane (meth)acrylate, spiroacetal (meth)acrylate, and polybutadiene (meth)acrylate, Oligomers can be mentioned.

Specific examples of such monomers or oligomers include polyether (meth)acrylate synthesized from 1,2,8-hexanetriol/propylene oxide/acrylic acid, trimethylolpropane/propylene oxide/acrylic acid; adipine 1%j /1,8-hexanediol/polyester (meth) synthesized from acrylic acid, succinic acid/trimethylolethane/acrylic S, etc.
Acrylate; triethylene glycol diacrylate, hexapropylene glycol diacrylate, neopentyl glycol diacrylate, 1,4-butanediol dimethacrylate, 2-ethylhexyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl methacrylate, ethylcarpitol Acrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, 2.2-bis(4-acryloyloxyjetoxyphenyl)propane, 2.2-bis(4-acryloyl) (meth)acrylate or polyol (meth)acrylate such as oxypropoxyphenyl)propane; diglycidyl etherified bisphenol A
/ Acrylic acid, diglycidyl etherified polybisphenol A / Acrylic acid, triglycidyl etherified glycerin / Epoxy (meth)acrylate such as acrylic acid:
γ-Butyrolactone/N-methylethanolamine/bis(4-incyanatocyclohexyl)methane/2-hydroxyethyl acrylate, γ-butyrolactone/N
-Methylethanolamine/2,8-) lylene diisocyanate/tetraethylene glycol/amide urethane (meth)acrylate such as 2-hydroxyethyl acrylate; 2,8-tolylene diisocyanate diacrylate, inphorone diisocyanate diacrylate,
Urethane acrylates such as hexamethylene diisocyanate diacrylate; spiroacetal acrylate synthesized from diarylidene pentaerythritol/2-hydroxyethyl acrylate; acrylated polybutadiene synthesized from epoxidized butadiene/2-hydroxyethyl acrylate; These polymers and oligomers may be used alone or in combination of two or more.

Among the above monomers and oligomers, the following general formula % formula % [wherein n is an integer of 1 to 4, and at least 3
8 represents a single bond, a polyoxyalkylene group having a fullkylene group having 1 to 8 carbon atoms, or a polyoxyalkylene group having an alkylene group having 1 to 8 carbon atoms, and the remainder is a group having 1 to 8 carbon atoms. Alkyl group, hydroxyl group, amine group, formula (OR9) @ -H (wherein, RQ is carbon a1
~8 fullkylene group, m is a positive integer. )
Group or formula represented by (OR9)m -0)1
In formula C, R9 and m have the same meanings as above. ), such as dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol pentaacrylate, tripentaerythritol hexaacrylate, tripentaerythritol Hebuta acrylate etc.
The following general formula (II) CH3 蓼X C)13 -CH2COCH2-OCO-CH-CH2...(I
I) Polyacrylates of the polybisphenol A type, for example diglycidyl etherified bisphenol A, where n is a positive integer from 1 to 10 and X is optionally -OH or -COCH-CH2. diacrylate, diacrylate of Epicote 61001 (n=3, manufactured by Shell), etc., or the following general formula (m) 0 0H3 -0(-XnO-x20-X+0-)-C-CH-CH
2-position...(m) (wherein, Xi l X2 ,..., Xn are the same or different alkylene groups having 6 or less carbon atoms, or have a structure in which one hydrogen atom thereof is replaced with a hydroxyl group, n is an integer of 0 to 5), such as 2.2-bis(4-acryloyloxydiethoxyphenyl)propane, 2.2-bis(4-acryloyloxytriethoxyphenyl)propane, 2 , 2-bis(4-acryloyloxydibropoxyphenyl)propane and the like have very good quick drying properties in air when ultraviolet rays are used as active energy rays, and are particularly preferred crosslinking agents.

A silicone surfactant and/or a fluorine surfactant are essential to prevent blocking with a color sheet (transfer paper) when performing thermal transfer with low energy. In other words, it has been found that in order to obtain a high concentration of color development by sublimable disperse dyes at low energy, it is sufficient to reduce the amount of the crosslinking agent of the present invention, but at the same time, blocking appears significantly. . However, it has been found that by adding a small amount of a specific silicone surfactant or/and fluorine surfactant to this, blocking can be significantly eliminated even if the amount of crosslinking agent is small.

Among silicone surfactants, compounds containing blocks of polydimethylsiloxane and polyoxyalkylene (which may be slightly modified with other functional 11@ groups) are effective, especially for CH3 in silicone surfactants. -(SiO
) The ratio of l12- group and one OR- group (R: alkylene residue) is CHs-(SiO)+zz-/-OR-21/1
0 to 110.1 are preferable because they are excellent in improving blocking properties and improving leveling properties when the composition is used as a coating agent, but surprisingly, these silicone-based surfactants do not improve dyeing density. It has also been found that the method is effective in improving the transparency of cured compositions. If a silicone surfactant is not added, the dyeing density will be poor or the cured composition will become white and cloudy. The preferred range of these is 115 to 110.2
is within the range of

As a specific example of a silicone surfactant, general formula (IV
), (V) CH3 zeCH3+ 5i-0)l-(P)y-R+
-(W)CH3 (in the formula, P is +CH2CH20)+CH2Cl0)T-
and CH3 m and n are 1, 2, 3. ..., and X and y are 0, 1, 2, 3, . ...represents the number of to
Takes the value nX+ny. R1 represents one, an alkyl group, an acyl group, an aryl group, an acetoxy group, etc.) (in the formula, Q is +
CH2)7-0-(CH20H20)y+ C82CH
O)y-R3CH3, where m and n are 1, 2, 3. A positive integer of...
Also, X and y are 0, 1, 2, 3. The number of ..., 2 is O
or represents a fli number of 1 to 5, formula % formula % R2 represents -H, an alkyl group, an acyl group, or a CHs aryl group; R3 represents -H, an alkyl group, an acyl group, or an aryl group; There are compounds represented by ), which represent an acetoxy group, etc., and it is also possible to use two or more of these in combination.

By applying the composition described above to the basic surface and curing it, it is possible to easily dye it with a sublimable disperse dye. polyoxyalkylene derivative 0.1~
It has been found that 30 parts by weight (based on the total of 100 parts by weight of the polyester resin and crosslinking agent) may be blended.

Considering the prevention of bleed-out from the composition cured with active energy rays, the polyoxyalkylene derivative should have a degree of polymerization of the polyoxyalkylene group of 5 or more, and the polyoxyalkylene derivative should be stable at room temperature. Preferably solid ones 0 For example, ethylene oxide adduct of bisphenol A, triester of ethylene oxide adduct of castor oil, triester of propylene oxide adduct of castor oil, ethylene oxide adduct of trimethylolpropane triester of polyethylene glycol, diester of polyethylene glycol, ethylene oxide adduct of hydrogenated castor oil,
Examples include solid ones such as a triester of a random adduct of castor oil with ethylene oxide and propylene oxide, and a diester of a propylene oxide adduct of adipic acid.

Further, the degree of polymerization of the polyoxyalkylene group of the polyoxyalkylene derivative is 5 or more, and the polyoxyalkylene derivative has a polymerizable acryloyloxy group or/and a polymerizable acryloyloxy group in the residue.
Compounds having methacryloyloxy and methacryloyloxy groups are more preferable in that they have excellent polymerization activity by ultraviolet rays, fix the polyoxyalkylene derivative in the composition, and prevent bleeding. Examples of these compounds include polyethylene glycol monoacrylate, Examples include polyethylene glycol monomethacrylate, polyethylene glycol diacrylate, polypropylene glycol monoacrylate, polyethylene glycol dimethacrylate, and phenoxypolyethyl glycol acrylate.

It is also possible to use one or more of these polyoxyalkylene derivatives in combination, and the blending ratio is 0 as described above.
．． A range of 1 to 30 parts by weight is suitable, but preferably 0
．． It ranges from 2 to 20 parts by weight. If the amount is less than 0.1 part by weight, the effect of improving the dyeing density will be small, and if it exceeds 30 parts by weight, these compounds may bleed onto the surface or conversely reduce the dyeing density.

When using tetrahydrofurfuryl acrylate, which has strong polymer solubility and low viscosity, as a component of the crosslinking agent, the composition of the present invention composed of the above components can be applied directly to coatings such as roll coating, barcode coating, and blade coating. However, in order to improve coating workability, a solvent such as ethyl alcohol, methyl ethyl ketone, toluene, ethyl acetate, dimethyl formamide, etc. may be added to these compositions to adjust the coating viscosity to an appropriate value. This makes it easier to apply spray coats, curtain coats, flow coats, tiraffe coats, etc.

Depending on the purpose for which the above composition is used, several grams may be added.
Fine aluminous particles of less than m in size, such as silica, alumina, talc, titanium oxide, etc., may be blended.

The composition of the present invention is cured by active energy rays such as electron beams and ultraviolet rays, but in consideration of radiation source control, it is preferable to use ultraviolet rays. It is preferable to add 0.1 to 10.0 fiQ parts of a photopolymerization initiator to the total weight of the polyester resin and crosslinking agent.
Specific examples of photopolymerization initiators include benzoin, benzoin iso-jf ether, benzyl dimethyl ketal, ethylphenyl glyoxylate, jetoxyacetophenone, 1,1-dichloroacetophenone, 4'-isopropyl-2-hydroxy-2-methyl. Propiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, benzophenone/jetanolamine,
4. Carbonyl compounds such as 4'-bisdimethylaminobenzophenone, 2-methylthioxanthone, tart-7'thylanthraquinone, and benzyl; TltL yellow compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; bisisobutyronidonyl , azobis-2,4-dimethylvaleronitrile, etc. (7)
7zo compound; benzoyl peroxide, g-tert
Examples include peroxide compounds such as -butyl peroxide, and these compounds may be used alone or in a mixed system of two or more.

Examples of articles to which the above composition of the present invention can be applied include cotton fabrics, PET films, and jt! Examples include bifilm, PMMA sheet, PC sheet, acrylic lens, polyester button, nylon buckle, paper, PP paper, etc. After the composition is applied by the above-mentioned coating method, it is cured with active energy rays. Ru.

[Example] An example of the present invention will be listed below and will be described in more detail.

In addition, in Examples and Comparative Examples, all “parts” refer to ffi.
Represents a site.

Reference example 1. Making a transfer sheet Kaya set blue 1 on a commercially available transfer paper with a thickness of 60Bm
A transfer sheet was prepared by uniformly applying a 5% trichlorethylene solution of No. 36 (manufactured by Nippon Kayaku).

Reference example 2. Dry heat transfer method Paper is placed on an ironing board, the resin composition of the present invention is coated thereon, the cured article is placed thereon, and the transfer sheet prepared in Reference Example 1 is placed thereon. Furthermore, the thickness is 85pm on top of this.
After layering commercially available paper.

145℃ on hot plate under pressure of 1 kg/cs2
Heat for ×10 seconds.

Reference example 3. Evaluation of Blocking Resistance After the dry heat transfer in Reference Example 2, when the dyed article and the transfer sheet were peeled off, the blocking resistance was expressed as "good" if the dyed article could be easily peeled off, and the dyed article was tacky. Items that required some force were designated as "r defective."

Reference example 4. Dyeing Density Measuring Method The dyeing density was determined by measuring the light transmittance T using a color analyzer (Model 307 manufactured by Hitachi, Ltd.) and calculating it as -1ogT.

Examples 1 and 2, Comparative Examples 1 to 8 After mixing and adjusting the compositions shown in Table 1, they were mixed at 1100 p.
It is coated uniformly on one side of a thick transparent polyester film (Lumirror manufactured by Toshi Co., Ltd., product number 100. Type 510) by the dipping method, and then irradiated with ultraviolet rays using a 2 kW high-pressure mercury lamp in the air to form a sublimable film with a film thickness of 4 JLm. Since disperse dye dyeable articles were obtained, evaluations were conducted according to Reference Examples 1 to 4. The results are shown in Table 1. Also, when the adhesiveness of the cured composition to the polyester film was tested using cellophane tape, the article of the present invention was found to be good and did not peel off.

PE0-DMA: Polyethylene glycol (degree of polymerization 23) dimethacrylate 2PCA Nidipentaerythritol hexaacrylate 2P5A Nidipentaerythritol pentaacrylate 2P4A Nidipentaerythritol tetraacrylate A-[IEP: 2,2-bis(4-7')!
j O4k years old * cydiethoxyphenyl) propane polyester resin A: Resin consisting of terephthalic acid/isophthalic acid/ethylene glycol/neopentyl glycol (molecule M: 15,000 to 20,000.g65
°C) Silicone surfactant A: H3 2m+n1//nx+ny = 2.5 Example 3゜875 parts of polyester resin, 10 parts of acrylic acid addition diacrylate of diglycidyl etherified bisphenol A, 5 parts of 2P6A, 5 parts of 2P5A, 5 parts of 2P4A 1 part, silicone surfactant B 5 parts, castor oil ethylene oside adduct triethyl ester 7 parts, photopolymerization initiator 2-
6 parts of hydroxy-2-methylpropiophenone,
After spraying a composition consisting of 300 parts of t/l/ene and 100 parts of methyl ethyl ketone onto white stockinette,
Curing was performed in air by irradiating ultraviolet light with a 2 kW high-pressure mercury lamp. When this was subjected to dry heat transfer according to Reference Example 2, it was dyed very well without blocking.

(Note) Polyester resin B: Resin consisting of terephthalic acid/sebacic acid/ethylene glycol/neopentyl glycol (molecular weight: 20000-25000.T glO ℃) Silicone surfactant B: CH3 2m+n+l/nx+B = 0.35 Example 60 parts of 4° polyester resin C, 5 parts of 2P6A.

2P5A 5 parts, 2P4A 5 parts, 2.2-bis(
25 parts of 4-acryloyloxydibropoxyphenyl)-propane, 04 parts of silicone surfactant, 8 parts of methoxypolyethylene glycol (degree of polymerization: 20) acrylate
parts, 5 parts of 2-hydroxy-2-methylpropiophenone, and 250 parts of ethyl acetate.

A composition consisting of 250 parts of methyl ethyl ketone was applied to a colorless methacrylic resin plate with a thickness of 1 mm by a flow coating method so that the film thickness after curing was 5 gm, and cured by irradiating ultraviolet rays in the air. When this was subjected to dry heat transfer according to Reference Example 2, it was dyed well without blocking and showed -1 part gT = 0.75.

(Note) Polyester resin C: Resin consisting of terephthalic acid/isophthalic acid/sebacic acid/ethylene glycol/neopentyl glycol (molecular weight: 20,000 to 25,000.T
g 10℃) Silicone surfactant C: l CH30-EH2CH20)y-CCOCH3)z2m
+n1//nx= 1.3 [Effects of the Invention] The composition easily dyeable with a sublimable disperse dye of the present invention can be easily dyed with a sublimable disperse dye at a high concentration, and has color development and clarity that are superior to conventional dyes. It is far superior to that of
The composition of the present invention has excellent blocking resistance and high heat resistance, and can perform dry transfer of disperse dyes at low temperatures and in a short time with low energy, so it can be used, for example, as a composition for dry transfer printing of textiles, It is extremely useful as a composition for dry thermal transfer of plastic molded products (films, sheets, lenses, buttons, etc.) and has great industrial value.

Claims (1)

[Scope of Claims] 1. 100 parts by weight of a mixture consisting of 40 to 95% by weight of a polyester resin and 60 to 5% by weight of a crosslinking agent that can be cured by active energy rays, and a silicone surfactant and a fluorine surfactant. At least one selected 0.01-10
parts by weight, and 0.1 to 3 parts by weight of the polyoxyalkylene derivative
An easily dyeable resin composition containing 0 parts by weight of a sublimable disperse dye. 2. The resin composition according to claim 1, wherein the polyester resin is a linear thermoplastic polyester resin obtained by polycondensation of a dicarboxylic acid and a diol. 3. The composition according to claim 1, wherein the polyester resin is an unsaturated polyester resin obtained by condensation polymerization of an unsaturated polybasic acid having a reactive double bond and a polyhydric alcohol. 4. The linear thermoplastic polyester resin is a resin obtained by polycondensation of two or more dicarboxylic acids and two or more diols, and has a crystallinity of 1% or less. Resin composition. 5. The resin composition according to claim 1, wherein the crosslinking agent contains at least one polyfunctional monomer. 6. The resin composition according to claim 1 or 5, wherein the polymerizable group of the crosslinking agent is a (meth)acryloyloxy group. 7. The main component of the silicone surfactant is a polyoxyalkylene modified product of polydimethylsiloxane, and CH_3
-(SiO)_1_/_2- and -OR- ratio is CH_3
-(SiO)_1_/_2-/-OR-=1/10~1
/0.1. 8. The resin composition according to claim 1, wherein the polyoxyalkylene derivative has a degree of polymerization of a polyoxyalkylene group of 5 or more, and the polyoxyalkylene derivative is solid at room temperature. 9. The polyoxyalkylene derivative has a degree of polymerization of the polyoxyalkylene group of 5 or more, and has at least one acryloyloxy group and/or methacryloyloxy group in the residue of the polyoxyalkylene derivative. A resin composition according to claim 1. 10. The resin composition according to claim 1, wherein the active energy ray is an ultraviolet ray. 11. Mixture 10 consisting of polyester resin and crosslinking agent
11. The composition according to claim 1 or 10, wherein 0.01 to 10 parts by weight of a photopolymerization initiator is blended with respect to 0 parts by weight.