JPS58103519A - Curable resin composition - Google Patents

Abstract

PURPOSE:A resin composition low in volume shrinkage in curing and suitable for protective films, prepared by mixing an unsaturated polyester comprising a pollycarboxylic acid mixture of a specified composition and a glycol with an ethylenically unsaturated bond-containing mixture and a polymerization initiator. CONSTITUTION:An unsaturated polyester is prepared which comprises a cyclic polycarboxylic acid containing at least three carboxylic groups (e.g. trimellitic acid), a dicarboxylic acid containing an ethylenically unsaturated groups (e.g., fumaric acid), a bulky alicyclic didcarboxylic acid containing at least two carboxyl groups (e.g., cyclohexanedicarboxylic acid) and a bulky glycol having a 50C or lower branched aliphatic chain or alicyclic chain (e.g., neopentyl glycol). Then, 40-80wt% this resin is mixed with 60-20wt% ethylenically unsaturated group-containing monomer (e.g., methacrylic acid) and a polymerization initiator to form the purpose curable resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a curable resin composition, II! More specifically, the present invention relates to a useful curable resin composition containing an unsaturated polyester as a main component and having reduced volumetric shrinkage upon curing.

Conventionally, various types of resin compositions that can be cured by light or heat to form coatings or other resin molded articles have been widely used, including resins, thermosetting resins, and photocuring resins. Among them, the number of tatami shops using photocurable photosensitive resin has been remarkable in recent years.
In particular, liquid photosensitive resins are used in a wide range of applications because of their high adaptability to a variety of uses due to their polymer design, their contribution to improving the working environment, and their economic efficiency such as their fast curing speed. However, in reality, these cured products do not satisfy all of the properties such as formability, adhesion, chemical resistance, and intellectual property. It is a well-known fact that 11 (peeling), warping, plate distortion due to flow K, etc. occur, and the performance of the obtained cured product often deteriorates.

It is known that unsaturated polyester resins usually undergo volume shrinkage of 7 to 12% during curing, which is considered to be one of their major drawbacks, even if they are thermally cured at #IK and light-cured at 11K. It is believed that this is due to a decrease in free volume due to crosslinking reaction of the molecular chains of the fins, and although many attempts have been made to solve this drawback, none have been found to be satisfactory.

For example, there have been attempts to blend long-chain saturated polymers as a molecular binder (Tokukoku Publication No. 7448/1983), but in reality, the volumetric reduction during curing of Kri is difficult due to the amount of F&D. There are many problems such as the need to incorporate a compound, compatibility with the crosslinking monomer, and viscosity of the liquid resin, making it impractical.

Furthermore, JP-A-51-511102 proposes an attempt to use 70-92% of a branched unsaturated polyester made of a polyhydric alcohol as a composition for a liquid photosensitive curing resin for printing plates.

However, in general, when considering the operability of liquid photosensitive resins, unsaturated polynisdelic acid accounts for 10 to 1! of the entire resin! −
If the photosensitive resin itself occupies less fluidity,
Special measures such as heating are required when operating the coating pad. [
K Also, 3fI among polyhydric alcohols to obtain a branched structure
Although 10 to 70 moles of the above alcohols are used,
This method also causes gelation during the unsaturated polyester synthesis reaction, requires a very long reaction time at low temperatures, or requires a two-stage reaction or the use of a catalyst, making it impractical in actual production.

The inventors of the present invention have arrived at the present invention as a result of intensive studies aimed at reducing the volumetric yield during curing in liquid resin composition 1 having an unsaturated polyester content (40 to 80% by weight), which is commonly used.

That is, Book 11@ is a curable resin composition consisting of a composition consisting of the following (2) and (2), and (0).

(2) Unsaturated polyester 40-80 obtained from polycarboxylic acid and glycol having the following compositions (1) to (4)
(1) Cyclic IIJ carboxylic acids having at least 3111 carboxyl groups or their reactive conductor groups, <2) dicarboxylic acids containing functionally unsaturated groups, (3
) at least one bulky alicyclic dicarboxylic acid having at least 2ill carboxyl groups or reactive derivative groups thereof; (4) branched aliphatic chains and/or chains having up to 50 carbon atoms; At least one volume of a bulky glycol having a Lu group chain; (B) 20 to 60% weight of an ethylenically unsaturated group-containing polymer having compatibility with the unsaturated polynisder; (Q) Characteristics of the present invention: polymerization initiator The following are listed below.

b) The cyclic polycarbonate of (4)-(1) above facilitates the control of acid during the synthesis of unsaturated polyester, and the obtained nine-unsaturated polyester resin has Of11M properties and Kll compatibility when added to a dilute alkaline aqueous solution. It is very effective in maintaining the

The ethylenically unsaturated group-containing carboxylic acid of 0)(2)-(R) plays the role of introducing an unsaturated group into the scissors-unsaturated polyester.

) → (g)-(3) The bulky alicyclic dicarboxylic acid is
A Wr ring group dicarzene acid having a cyclohexane ring, cyclohexe/lK% or piacro ring is preferable as a component that exhibits an extremely large effect on reducing volumetric shrinkage during curing, which is the object of the present invention.

2) The bulky glycol having 50 or less carbon atoms in (4)-(4) is a component that has a great effect on reducing curing shrinkage, which is the objective of the present invention, and is a branched aliphatic chain glycol. The aliphatic chain glycol contains at least 4 tons of hexane and has a carbon atom number of 16 or more, and if it has a structure in combination with a branched aliphatic chain, it is more than 1 ltL.

When it comes to the glycol component, especially the glycol component, the effect of reducing hardening, which is the objective of the present invention, is better achieved by using it alone or in combination with some of them. Therefore, moisture resistance, chemical resistance, 15Il
It is also possible to improve properties such as Ia properties.

e) The ethylenically unsaturated group-containing monomer in (2) is what is generally called a "crosslinking monomer"! +, A cured product with a three-dimensional structure is obtained by a crosslinking reaction with the unsaturated polyester (A). Good compatibility with the unsaturated polyester is an essential condition; if the compatibility is insufficient, phase separation, peeling, etc. will occur in the cured product after crosslinking, making it impossible to use.

f) The polymerization initiator in (C) also includes thermal polymerization initiators and photopolymerization initiators (so-called sensitizers).

The curable resin composition W of the present invention can be thermally cured or photocured 41Tl.
l! Regardless of which curing method is used, the above-mentioned cured product with excellent low yielding properties can be obtained.

In particular, in the case of photocuring, its advantages can be greatly utilized, such as short curing time1, improved workability, and thermal distortion (
Among the unsaturated polyester components used in the present invention, which can prevent reaction) or coloration (yellowing), [specific examples of cyclic polycarmene buttons having at least three carboxyl groups or reactive derivative groups thereof] Examples include nidrimesic acid, trimellitic acid, hemimellitic acid,
acid, pyromellitic acid, 346-) luentric acid, L&! s-) Limethyl-λ46-benzenetricarboxylic acid, penzophenone detracal g7e% ethylene bistrimellitic acid, naphthalene tricarboxylic acid,
Naphthalene tricarboxylic acid, anthracene tricarboxylic acid, anthracene tetracarboxylic acid, triphenylmethane tricarboxylic acid and acid anhydrides from these.

Specific examples of the "ethylenic unsaturated group-containing dicargen" include maleic acid, fumaric acid, citraconic acid, menaconic acid, itaconic acid, and reactive conductors thereof.

Specific examples of "bulky alicyclic dicarboxylic acids having at least two carboxyl groups or reactive derivative groups thereof" include: sahydrophthalic acid, detrahydro7thalic acid, Bicyclo[2λ1]-5-hepden-λ3-dicarboxylic acid, bicyclo[zzz]-s-octene-λ3-dicarboxylic acid, cyclohequinanedicarboxylic acid, lower alkyl group substituted products such as methyl and ethyl, 2-methyl -hexene-l-λ45-tricarboxylic acid and anhydrides of these polyhydric carmenic acids.

Among [bulky glycols having a branched aliphatic chain or aliphatic chain having a carbon atom of aSO or less], the "bulky glycols having an aliphatic chain" include branched glycols having a lower alkyl substituent. A concrete example of this can be found in the following commercially available products: Neobentyl Glycol,! -Methyl-tomi-n-propyl-1,3-propanediol, LLII-trimethyl-1,3-propanediol, λλ4-) Q Methyl-L3-penta/diol%2-methyl-1,5-bentanediol, LL, 44-tetramethylbutanediol, glycerin monoallyl ether, etc.

In addition, [high bulk glycol having an alicyclic chain] is defined as having at least 1') cyclohexane ring, or having one cyclohexane ring, and combined with a branched aliphatic chain. The following are specific examples of glycols with a specific structure: Hydrogenated bisphenol-A, 1,4-cyclohexane dimetatool, ethylene oxide adduct of hydrogenated bisphenol (2 -10 mol), cytoadduct of hydrogenated bisphenoroome in propylene (2-10 mol).

Book At11! [Ethylenically unsaturated group-containing monomer compatible with unsaturated polyester] is an ethylenically polymerizable monomer that acts as a diluent for unsaturated polyester and is polymerizable with at least VC of unsaturated polyester. Those having one or more unsaturated groups, including methacrylic acid, methacrylic talolide and methacrylic esters, acrylic acid, acrylic chloride and acrylic esters, vinyl esters, methacrylamides, acrylamides. , vinyl ethers, styrene and its derivatives, and allyl compound-1N-vinyl compounds.

Specific examples of methacrylic acid esters include: methyl methacrylate, methyl methacrylate, n-propyl methacrylate, isobutyl acrylate, n-
Butyl methacrylate, inbutyl methacrylate), 5
ea-butyl methacrylate, t-butyl methacrylate, 7-talohexyl methacrylate, benzyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, methoxyethyl methacrylate, diethyl methacrylate in methacrylate,
Butoxyethyl methacrylate, methoxypolyethylene glycol methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, human ol? diptyl methacrylate, hydroxypentyl methacrylate, hydroxychlorogribyl methacrylate, polypropylene glycol methacrylate), N,M-diethylamino methacrylate, M,M-diethylamino methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, riooethyl methacrylate, diprom Globil methacrylate, tribromtzenyl methacrylate, allyl methacrylate, oleyl methacrylate, epoxystearyl methacrylate V-),
) Limethylolpropane monomethacrylate V-), diethylene glycol monomethacrylate, pentaerythritol monomethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1
．． 3-butylene glycol dimethacrylate), 1. @-
Hexane glycol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, diglycerin dimethacrylate, starbis-(4-methacryloxyethoxyphenyl)propane, λ2-bis(4-methacryloxyjethoxyphenyl)propane, trimethylol propane trimethacrylate etc.

Specific examples of acrylic esters include: methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, θθC-butyl acrylate, t-butyl acrylate, fuchlorohexyl. acrylate, hydroxylauryl acrylic V-)
, benzyl acrylate, 2-ethylhexyl acrylate, carpitol acrylate, metoya ethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, metoya polyethylene glycol acrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, hydroxyethyl acrylate, butylene glycol monoacrylate), N, N
-dimethylaminoethyl acrylate), IJ, 11-diethylaminoethyl acrylate, glycidyl acrylate, detrahydrofurfuryl acrylate, lysylroethyl acrylate, dibromopropyl acrylate, tribromphenyl acrylate, allyl acrylate,
Epoxy stearyl acrylate, polyethylene glycol diacrylate, LS-butylene glycol diacrylate, LS-butylene glycol diacrylate,
LS-hexane/Q cold diacrylate, neopentyl glycol diacrylate, diglypylene glycol diacrylate, polypropylene glycol diacrylate, λ2-bis(4-7 cydiethoxyphenyl)propane, λ2-his(4-acryloxy) Gribilokiku 7 Koji”) FuC1 Han, trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacryl formal, tetramethylolmethane detraacrylate, etc.

Examples of the vinyl esters include vinyl butyrate, vinyl trimethyl acetate, vinyl carbonate, vinyl acetate, vinyl salicylate, divinyl succinate, divinyl phthalate, and the like.

Examples of methacrylamides include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-arylmethacrylamide, and N-hydroxyethyl-N-methylmethacrylamide; examples of acrylamides include acrylamide, N-'t
-butylacrylamide, Nt-octylacrylamide, N-methylolacrylamide, H-butoxymethylacrylamide, N-isobutoxymethylacrylamide, diacetone acrylamide, and the like.

Examples of the vinyl ethers include alkyl vinyl ether types such as hexyl vinyl ether, octyl vinyl ether, ethylhexyl vinyl ether, vinyl aryl ether type vinyl phenyl ether, and polyhydric alcohol polyvinyl ether.

Examples of the styrene conductor include styrene and divinylpene having substituents such as alkyl, alkoxy, norogen, carboxyl, and allyl groups at the ortho and/or para positions.

Allyl compounds include diallyl esters of dicarboxylic acids, and specific examples include diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl hexahydro-7-thaleate, diallyl-hydroisophthalate, and diallyl-hydroisophthalate. Examples of triallyl esters of tricarboxylic acids include triallyl trimellitate and the like.

and -vinyl compounds include y-vinylpyrrolidone, y
-vinylimidazole, N-vinyloxazolidone, N
- It can produce compounds such as vinyl carbazole.

In the present invention, the amount of unsaturated group content used is usually 20 to 60 parts by weight per 100 parts by weight of the unsaturated polyester resin.
The amount is preferably 30 to 50 parts by weight.

If the amount used is too large, the properties of the cured product such as solvent resistance, chemical resistance (acid, alkali), flexibility, heat resistance, etc. will be reduced. On the other hand, if the amount is too small, the viscosity will be difficult to control and the operability of coating etc. will be poor.

The "polymerization initiator" K that can be included in the resin composition of the present invention is an initiator used in general thermosetting resin compositions and an initiator used in photocurable resin compositions. It includes a wide range of agents.

Examples of the thermosetting initiator include organic peroxides and azo compounds such as hydrocarbons, ketone peroxides, dialkyl peroxides, diacyl peroxides, and peroxy esters.

Specific examples of organic peroxides include penzoyl peroxide, di-t-butyl peroxide, methyl ethyl ketone peroxide, cumene hydrocarbon, etc. Specific examples of azo compounds include azo Examples include bisinobutyronitrile.

In addition, the above-mentioned organic peroxides and azo compounds can be used as photocuring initiators, and carbonyl compounds, organic sulfur compounds, halogen compounds, photoreducible dyes, etc. can be used as waste sensitizers.

Specific examples of carnyl compounds include benzine,
Benzoin methyl ether, benzoin ethyl needle, penzoin isoglibyl: L-, fk, benzoin ibutyl ether, benzophenone, anthraΦone,
Benzyl dimethyl ketal, etc., and organic sulfur compounds such as dibutyl sulfide and benzyl sulfide.
Examples of halides include carbon tetrachloride, and examples of photoreducible dyes include erosin, elysium, and methylene blue.

The resin composition of the present invention can be cured by heat or light, but in some cases it can be cured by irradiation with ionizing radiation such as electron beams or radiation, and in this case, the above-mentioned polymerization initiator may be used. may not be intentionally included in the composition.

The amount of the polymerization initiator used is usually 105 to 15 parts by weight, preferably α1 to 5 parts by weight, based on the total amount of the unsaturated polyester resin of the present invention.

i9. Along with such a polymerization initiator, a polymerization accelerator can be included in the composition, if necessary. K includes conventionally known amines, amphuketones, aminobenzoic acid esters, 7-osphines, and thioalcohols such as 2-mercaptobenzimidazole.

Examples of rich inhibitors that can be used in the resin composition Kt8S)XJ of the present invention include hydroΦnon, p-methoxypher/-
Examples include t-butylcatechol, hyrogallol, phenothiazine, naphthylamine, diphenylamine, N-nitrosodiphenylamino, and p-toluidine.

The amount used may be generally aoos-z parts by weight based on the total amount of the unsaturated polyester resin of the present invention.

In addition to the above-mentioned components, the cured resin composition of the present invention includes
l! Conventionally known fillers, technotropic agents,
Additives such as plasticizers, defoamers, and colorants can be blended. The filler can be used in a range of usually from as to 10 parts by weight based on the total amount of the unsaturated polyester resin, and the other additives can be used in a range of usually from αOS to 10 parts by weight based on the total amount.

When curing the cured resin composition of this 4h #4, this composition is rolled up with various coverings that have good formability, or subjected to appropriate casting treatment, etc. , heating, irradiation with active light, or irradiation with ionizing radiation as the case may be. The most desirable method is photocuring using actinic light such as ultraviolet rays, which has many advantages such as shortening the curing time and significantly preventing warping and yellowing during curing 1.

As mentioned above, the cured resin composition of the present invention reduces volumetric shrinkage during curing and provides good properties of the cured product, so that it can be used as a protective coating material for electrical insulating materials, paints, adhesives, photoresist materials, and photosensitive materials. Not only can it be used for a wide range of applications such as flexible resin boards, displays, and laminated materials, but it can also be used for various other types of hardening molding, such as fiber processing, reinforcing and protecting plastics and glass, etc.
You can also use K such as gold #j4 face up.

EXAMPLES The present invention will be explained in detail and concretely using examples below. In addition, "part" in the examples means "part by weight", and "acid value" is "milligrams of potassium hydroxide required to neutralize 1 gram of sample".

Moreover, the volumetric shrinkage rate 1 was calculated using the following formula.

Volumetric shrinkage rate -- Parts of Tal, 1511 parts of diethyl V7 glycol, 2011 parts of neopentyl glycol, and 41111 g of a propylene oxide adduct (4 moles) of hydrogenated bisphenoroom were mixed at 100 to 130°C under a nitrogen atmosphere for αS time, then tSO ~ 210℃
An unsaturated polyester of acid@121 was synthesized by reacting for AS time.

65 parts of this unsaturated polyester, 6 parts of methacrylamide
part, diallylisophthalate 29 parts, benzoin ethyl ether LO part, 2-mercagutopenzimidazole a
A photocurable resin composition was obtained by mixing 045 parts of 0.045 parts and 018 parts of ditrodiphenylamine a (resin composition).
.

Resin B was prepared in exactly the same manner except that 29 parts of diallyl hexahydrophthalate was used for the incubation using diallyl iso-7thalerate.

Similarly, Resin C and Resin "Comparative I" were obtained by conventional methods as shown in Table 1.

These nine resins obtained were photocured in the following manner.

That is, a negative film is placed on a glass plate set horizontally, a 9 micron thick polyethylene terephthalate film is placed on top of it, and a K11k cloth with a thickness of K11k made of resin composition α1■ shown in Table 1 is placed on top of it. did. Next, α11! was applied on top of this resin. ! Layer the polyethylene terephthalate film and place it in a negative film box.
A light source consisting of eight fluorescent lamps was used to illuminate the area for 5 minutes.

The unexposed area was removed by washing with a dilute alkaline aqueous solution and then dried. It was sufficiently hard and strong.

The densities of the cured resins and resin liquids shown in Table 1 were all measured, and the volume shrinkage rates were calculated and shown in Table 1.

Book! & The volume shrinkage of the resins B and 0 of the clear example is significantly lower than that of Comparison 1.

Example 2 As shown in Table 2, the charged molar ratio of 7-maric acid, trimellitic anhydride, hydro-7-talic anhydride, diethylene glycol, and an ethylene oxide adduct of hydrogenated bisphenoroom (2 moles) was 0:20:20:60:
30 (acid value 141)) and 7-
An unsaturated polyester (acid value 150) in which the molar ratio of r-ruic acid, trimellitic anhydride and diethylene glycol was 80:20:90 was synthesized in the same manner as in Example 1 according to the Kempo method. Comparison 2. Comparison of IC and resin resins with the compositions shown in Table 2 from two types of unsaturated polyesters. Comparison 3 was prepared.

The obtained four types of resins were irradiated with ultraviolet rays in the same manner as in Example 1 to obtain cured products. All had sufficient hardness and strength.

The volume shrinkage rate is calculated from the density of the cured product and the resin liquid, and the second
Shown in the table.

1 In addition, the warp h (m) is determined by KID as shown in Figure 1, and the relief punch line L←) is measured as shown in Figure 21.9. However, in the figure, 1 indicates a cured resin, and 2 indicates a steel plate.

The warpage h (■) test piece was prepared and measured as follows.9.

That is, in addition to the exposure process K in Example 1, a similar process was carried out using a 431111 steel plate having a wrinkle prevention layer and an adhesive layer instead of the Al 25 film overlaid on the resin. I made a fully cured version of the lQem square. When the cured product side is facing up, a concave warp appears, so the depth h(-) was measured and defined as the "warp" in this case.

The results are shown in Table 2. The less anti-Shi, the better.

In addition, the voice of the relief was determined by K as follows.

That is, in the exposure treatment of Example 1, a negative film having a S-shaped plate was used, and an α3-marin steel plate was used in the exposure treatment in the same manner as the warped test piece above.

The obtained cured product has a three-dimensional image of diameter ham% bird size αγ■ (
The center part of the upper surface is concavely lower than the periphery (edge) K, and the difference in height L (s) is defined as the "punch line of the relief" in this case. The results are shown in Table 2. This Ochoco has a small m*<, and when used as a cured full printing plate, clear printed matter with less fading etc. can be obtained.

2nd I! l! From the results, the resin resin and E of the present invention example are as follows:
Comparison of comparison 2 and comparison 3 tree mlK ratio, volumetric shrinkage rate,
The results were excellent both horizontally and vertically.

Example 3 Four types of unsaturated polyesters having the molar ratio shown in Table 3 were synthesized according to a conventional method, and 76 parts of each unsaturated polyester,
4 parts methacrylamide.

20 parts of diallyl phthalate, 17 parts of benzoin methyl ether, 2-mercagutopenzimidazo-k (104
Resins F, G, H and Comparative 4 were obtained, each consisting of 1 part and 0f part of p-methoxyphenoluminium.

Example 1 except that a 2KN high-pressure mercury lamp was used instead of a %SOW UV full-light lamp when exposing these resins.
Each cured product was obtained by exposure in the same manner as above. All of these cured products had sufficient hardness and toughness.

The volumetric shrinkage rate was calculated from the density of the obtained cured product and resin liquid, and is shown in s*. Resin of the present invention example? , G, and II all have lower volume shrinkage rates than the comparative example resin (comparison 4).

#s 3 Table However, Honkawa #1lIiiiIFcp%Ae-HA: Anhydrous methic A/ /% imitsucic acid (Hitachi Chemical), MPPD:
2-Methyl-2-n-propyl-1,3-propanediol, TMPD: L L 3-trimethyni-IJ
-Propanediol, 1lIQ-40: ethylene oxide 4 mole adduct of hydrogenated bisphenoroome, icG:
ethylene glycol.

No. 5llI! Both resins contain 7 parts of benzoin methyl ether a, 2-mercaptobenzimidazole α0
4 parts and 101 parts of p-methoxyphenol.

Example 4 Acid and glycol having the composition (charged molar ratio) shown in Table 4 were used as reaction components, and the reaction was carried out at 100 to 130°C for about 1 hour in an N snow atmosphere.
110N at 220° C. for about 7 hours to synthesize unsaturated polyesters having the nonacid values shown in Table 4. Next, this unsaturated polyester was dissolved in styrene monomer to prepare a solution having a resin content of 70 and 45 kg, respectively, and a mixture of non-α02Si [as shown in Table 4] was added and mixed as an inhibitor. Ninety-six types of unsaturated polyester resins were obtained.

These 1118 were heated at 60 to 75℃ in a glass partition plate.
A cured test piece having sufficient hardness was obtained by heating at 150°C for 3 hours and 2 hours at 150°C. The volumetric shrinkage rate was calculated from the density of this cured product and each Fti liquid and is shown in Table 4. Resin J-M of the present invention example had an extremely low volumetric shrinkage rate compared to Comparisons 4 and 5.

However, Book #4 IIA Book PG: Propylene 13 j-
Ago-go: ethylene oxide adduct of hydrogenated bisphenoroome (8 mol).

All of the resins in Table 4 are non-α02 in Hydro! ! part and benzoyl peroxide aS part.

[Brief explanation of the drawing]

The drawings illustrate a method of measuring the effectiveness of the invention. ,+1 daily dose 2 meals procedure amendment (method) % formula % 1, case display special application as! 00828 No. 2, Name of the invention Curable resin composition 3, Relationship with the person making the amendment ＼Patent applicant 1-11 Minamihonmachi, Higashi-ku, Osaka (300) Teijin Ltd. Representative Tomoo Tokusue 0) Details Add the following sentence after the 9th line of page 35 of the book. [Figure 1 is a diagram showing the method for measuring warpage h (as), and Figure 2 is a diagram showing the method for measuring warpage h (as), and Figure 2 is a diagram showing the method for measuring warpage h (as). It is a figure showing the measuring method of (#). In the figure, 1 indicates a cured resin, and 2 indicates a steel plate. Also, h is the depth of the sled, and j is the ssl of the ochoco! shows. "that's all

Claims (1)

[Scope of Claims] L A curable resin composition comprising a composition comprising the following (2) and (2) and (C). (~Unsaturated polyester 40-80 obtained from polycarboxylic acid and glycol having the compositions (1) to (4) below
(1) Cyclic polycarboxylic acid having at least three carboxyl groups or reactive derivative groups thereof, (2) Ethylenically unsaturated group-containing dicarmenic acid, (3
) At least one type of bulky alicyclic dicarponic acid having at least 21m carboxyl group or its reactive aggregate group, (4) Number of carbon atoms! At least one type of bulky glycol that supports 10 or less branched aliphatic chains and/or alicyclic chains; Ethylenically unsaturated group-containing phosphor having compatibility with Japanese polynisder 20 to 60 weight 1! : (03 Polymerization - Initiator 2 The curable resin composition according to item 1, wherein (3) of the above (A) has a cyclohexane ring, a cyclohexene ring, or a bicyclo ring. 1 The curable resin composition of the above (4) ) The curable resin composition according to item 5 or 2, wherein (4) has at least one cyclo linker and has 16 or more carbon atoms. The curable resin composition according to any one of paragraphs 1 to 3, wherein (1) is trimellitic acid or trimellitic anhydride.i) (2) of (g) above is fluoric acid. The curable resin composition according to any one of Items 1 to 4. Curable resin composition for any of the carpets. 7. The curable resin composition according to any one of items 1 to 6, which is photocurable.