JPS6259657A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent environmental stress cracking resistance and is freed from the problem of laminar peeling, consisting of a rubber-contg. styrene resin and a copolymer. CONSTITUTION:100pts.wt. acrylic ester monomer (e.g., methyl acrylate) or mixture thereof with other monomer copolymerizable therewith (e.g., styrene) and 0.01-10pts.wt. bifunctional long-chain monomer of formula I [wherein R<1>, R<2>, R<6>, R<7> are each H, CH3; X is -(CH2)l (CHR<3>)m(CR<4>R<5>)n and/or a group of formula II; R<3>-R<5> are each alkyl, aryl, alkoxyl, hydroxyl; Y is -O-, -S-, -SO2-, -CH2-, alkylidene, alkylene; l, m, n, x, y are each 0 or greater; l+m+n=5 or greater] are copolymerized to obtain a copolymer having a solubility parameter of 8.4-9.8(cal/cc)<1/2>, a glass transition temp. of 20 deg.C or below and a gel content of 70wt% or below. 1-50pts.wt. said copolymer and 100pts.wt. rubber-contg. styrene resin (e.g., ABS resin) are melt-kneaded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Tumor Application] The present invention relates to a thermoplastic FR resin composition that has excellent environmental stress cracking resistance and improved delamination properties.

[Conventional technology]

When im-containing styrenic resins come into contact with chemicals under stress, cracks occur, and in severe cases, they often break. This phenomenon is called environmental stress cracking phenomenon.
It is well known that high solubility in resins is observed in chemicals such as alcohols, carboxylic acids, esters, alkalis/alkenes, etc.

Environmental stress cracking occurs even when no external force is applied to the resin molded product, because the distortion in the bottom shape of the molded product is released by contact with chemicals. The content of the rubber component and the molecular weight of the bare component are known factors that have no effect on the environmental stress of rubber-rich styrene resin, which places great restrictions on the uses of styrenic resin. However, improvements to the environmentally stressed pillars have been achieved by increasing the W content of the rubber component or by increasing the molecular weight of the multilayer component, but the effects have been insufficient for practical use.

Recently, the present inventors have discovered that by mixing an acrylic acid ester polymer with an im-rich styrene resin, the environmental stress cracking of 1co9m-containing stainless steel yarn can be dramatically improved. (1!l Publication No. 58-179257).

However, although the composition of the invention has a remarkable effect of improving the environmentally stressed pillars, a matrix-like layered structure (separation phenomenon) may be observed in the injection molded product, and improvement is still needed. The zero-layer peeling phenomenon is noticeable in molded products injection molded under flat shear rate conditions, and is noticeable near the date.

The layered structure is caused by the acrylic acid ester polymer particles dispersed in the rubber-containing styrenic resin being flattened by shear stress during injection molding. For the purpose of preventing flat deformation of acrylic ester polymer particles, it is effective to copolymerize a polyfunctional vinyl monomer during polymerization of the acrylic ester polymer.

[Problem that the invention seeks to solve]

However, with acrylic ester polymers obtained by copolymerizing polyfunctional vinyl monomers such as sovinylbenzene and ethylene glycol dimethacrylate, although the delamination phenomenon is improved, the gel content is low. The improvement effect of rubber-containing styrene thread dark resin on environmentally stressed pillars is insufficient. For this reason, by using a polyfunctional vinyl monomer and a chain transfer agent in combination to produce an acrylic acid ester polymer with a low gel content and a branched structure, we are able to prevent layer delamination and environmental resistance. Although it is possible to measure the balance of stressed columns, the effect is unsatisfactory in practical terms.

The object of the present invention is to provide a thermoplastic multilayer composition which overcomes the drawbacks of the above-mentioned conventional techniques.

[Means for Solving the Problems] To summarize the present invention, the present invention relates to a thermoplastic resin composition, comprising (AJ rubber-containing styrenic night fat and (
8) copolymer, said (A) component 1o.

In a thermoplastic IR resin composition containing 1 to 50 parts of the tBl component based on the coulometric part, the copolymer of the component (B) has an acrylic ester ratio of 1 to 50 parts per coulometric part, or acrylic ester monomer. Mixture with other copolymerizable monomers 100
In the heavy filter part, the following general formula I:c formula, Ryu and R2 are H or CH3 group, Xk@-(CH2)4(CHR3) (
CR4R5) n-group (a, m and n are each an integer of 0 or more, and /10m+n is an integer of 5 or more, R3,
R4 and R5 are an alkyl group, an aryl group, an alkylene group, or a hydroxyfur group) and/or (X and y are each an integer of 0 or more; R6 and R'&
X H or t's CH3 group r) 1. fY tX-
0-3-s-1-SO, -1-CH2-, alkylidene group or alkylene group) is copolymerized with 0.01 to 10 parts of a long chain bifunctional monomer. The m solution antiparameter obtained by
It is characterized by being a copolymer having a glass transition temperature of 20°C or less and a Del content of 70% by weight or less.

The resin composition of the present invention has excellent environmental stress resistance and is less likely to cause delamination.

Monomers constituting the rubber fraction of the BIM-containing styrenic resin, which is component (A) in the present invention, include sitadiene,
Conjugated ZOE/jllLt bodies such as inoprene, zotylgutazoene, chloroprene, cyclopentadiene, 2,
5-norpornasien, 1-4-7 cucuhekitezoene,
Non-conjugated diene monomers such as 4-ethylidene norbornene, styrene, α-methylstyrene, vinyltoluene natonos fV7 spinning wheel, nitrile monomers such as acrylonitrile and metacyclonitrile, methyl methacrylate,
These include (meth)acrylic acid ester monomers such as ethyl acrylate, butyl acrylate, hexyl acrylate, and octyl acrylate, and olefin monomers such as ethylene, fovin, 1-butene, isobutylene, and 2-butene. These materials are used by homopolymerizing or copolymerizing them. In addition, a copolymer obtained by copolymerizing a polyfunctional vinyl monomer can also be used as a crosslinking monomer, but an example of a polyfunctional vinyl monomer that can be used is divinylhene. Sen, ethylene glycol dimethacrylate, 1゜6-butylene glycol dimethacrylate, 1゜4-ethylene glycol dimethacrylate, demipyrene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, allyl acrylate, allyl Examples include methacrylate, vinyl acrylate, vinyl methacrylate, glycisol acrylate, and glycisol methacrylate.

The rubber fraction A used as the prisoner component of the present invention must have a graft active site, and specifically, it is preferable that the rubber fraction has a carbon-carbon double bond in the rubber molecule. .

There are no particular limitations on the method of polymerizing the monomers (emulsion polymerization, emulsion polymerization, etc.).
Known techniques such as m-liquid polymerization can be used.

(The AJ acid component rubber fraction does not need to be one type, and may be a mixture of separately polymerized rubber components of the Yujihashi type or higher.

The monomers constituting the im-containing styrenic fat resin component (A) in the present invention include styrene, α
- Styrenic monomers such as methylstyrene, vinyltoluene, and t-glylstyrene; nitrile monomers such as acrylonitrile and methacyclonitrile; ) Acrylic acid ester monomer, maleimide, N-methylmaleimide, N-ethylmaleimide, N-7'rohilmaleimide, N-cyclohexylmaleimide-1N-7x nilmale (mil', N-tolylmaleimide, N- -IZ
There are manimir type monomers such as reel maleimy, which can be used alone or in copolymerization, but it is essential to contain a styrene type monomer.

The AJ acid component used in the present invention is composed of a rubber component and a resin component as described in 5 above, and a graft structure is present at the interface between the rubber component that has a spherical structure and the resin component that is a continuous phase. It is known that such a structure can be achieved by a so-called graft polymerization method in which part or all of the monomers constituting the resin component are polymerized in the presence of a rubber fraction. (AJ acid component known graft polymerization technique) of the present invention.

It can be manufactured by technique.

(In order to adjust the content of the rubber component contained in the AJ component, it is also possible to mix a separately polymerized +m fat component with the (A) component, but the separately polymerized resin component can be graft polymerized. It is not necessary that the composition be the same as that of the AJ acid component. The resin components obtained can be mixed.

Specific examples of the (N component) of the present invention include high impact folystyrene, ABS (acrylonitrile loose tuffene),
styrene) resin, heat-resistant ABS (acrylonitrile-gutazoene-sterene-α-methylstyrene) resin, AA
Examples include S (acrylonitrile-acrylic acid ester-styrene) resin, AES (acrylonitrile-EPDM-styrene) resin, and MBAS (methacrylate-detazoene-acrylonitrile-styrene) resin.

Examples of acrylic acid ester monomers used as raw materials in the method for producing the copolymer, which is component (B) of the present invention, shown at the arrow include methyl acrylate, ethyl acrylate,
butyl acrylate, hexyl acrylate, 7 chlorohexyl acrylate, octyl acrylate, hydroxyethyl acrylate, methoxy 7 ethyl acrylate,
Examples include phenyl acrylate and glycizol acrylate.

On the other hand, examples of other copolymerizable monomers include styrene, α
- Styrenic monomers such as methylstyrene and t-butylstyrene; nitrile monomers such as acrylonitrile and methacrylate; methacrylic acid ester monomers such as methyl methacrylate, butyl methacrylate, and glycysol methacrylate; styrene; Examples include monodispersed olefins such as 1-butene, isobutylene, and 2-butene, and ζ-nyl ether monomers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and phenyl vinyl ether.

In addition, component (B) of the present invention requires copolymerization of a long chain difunctional monomer, and the long chain difunctional monomer is represented by general formula I here.

[General formula I]

[In the formula, R1 and R2 are H or CH3 group, X is -(CH2
)□(CE(R'), CCR'R5) n-group (jSm
and n are each an integer greater than or equal to 0, and l + m +
n is an integer of 5 or more; R3, R' and R5 are an alkyl group, aryl group, alkoxyl group or hydroxyl group) and/or (X and y are each an integer of 0 or more; R6 and R7 is H or CH3 group, /Y is 10-1-day, -8o
, -1-CH2-, an alkylidene group or an alkylene group] Specific examples of X are -cH2-cH2-cH2-ca2-c
H, -1-C'H2-CH2-C'H2-CH2-CF
(2-CH8-5-CF (2-upper 2-upper 2-da 2-α-
1CH3 -CH2-CH2-CH2-CH2-C'H-C is also -1
-I upper 2-CH2 2 2 Tsukuda Qi, H -CH2-CH2-CH2-C'H2-C'H2-(1
'H2-C'H2-C'H2-1-CH2-CH2-C
H2-CH8-CH2-CH2-CT(2-CF(,-
CH2-CH2-1-CH, -CH2-CE(2-CF
(2-CF(-CH2-1H3, etc.), and specific examples of the compound represented by the general formula (2) include CF(3 CH3 CH2CHza-0-C-Cm CH2, etc.).

These long chain bifunctional monomers may be used alone or in combination of two or more.

The amount of the long-chain difunctional monomer used is 0.01 to 10 parts by weight, particularly preferably 0.01 to 7 parts by weight, based on 100 parts by weight of the monomers to be copolymerized as described above. However, if this amount is less than 0.01 parts by weight, the effect of improving layered peeling will be poor, while if it exceeds 10 parts by weight, the effect will be saturated.

Moreover, in addition to the long-chain bifunctional monomer, other polyfunctional vinyl monomers may be copolymerized with the component (B) in the present invention. Examples of convenient polyfunctional vinyl monomers include divinylbenzene, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, delobylene glycol zomethacrylate, quanul. Examples include triallyl acid, triallyl isonoanurate, trimethylolpropane trimethacrylate, allyl acrylate, allyl methacrylate, vinyl acrylate, and vinyl methacrylate.

Component (B) of the present invention has a content of 8.4 to 9.8 (cal/
cc) It is necessary to have a degree of sensitivity parameter of
lμ) 1i. As used herein, the term "resolution parameter" refers to the term "resolution parameter" as used in this specification.
up) and ear r-gut ('E,, H, Imme
rgut) @, Polymer Handbook (Polym
er Handbook) 2nd edition IV-337~■
Using the bath solubility parameter value described on page 659, the bath solubility parameter δT of the copolymer is calculated as follows: m freshness parameter δyu and its polymerization fraction W.

It is calculated using the following formula H.

The mwI degree parameter of gtylated polyacrylate and ethyl polyacrylate was 8.8 (caJ/
cc)”/2 9.4 (caJ%→1i),
The bath solubility parameter of a copolymer consisting of 70% by weight of butyl polyacrylate and 60% by weight of ethyl polyacrylate is 9. Q (cachahi) is calculated as 3/2.

If the bath solubility parameter of component (B) is less than 8.4 or more than 9.8, the environmental stress cracking resistance of the resin composition of the present invention will be low, which is not preferable.

Component (B) of the present invention needs to have a glass transition temperature of 20°C or lower, preferably 10°C or lower. When the glass transition temperature exceeds 20° C., the environmental stress resistance of the resin composition of the present invention becomes undesirable.

Furthermore, component (B) of the present invention has a del content of 70% by weight.
It is necessary that the following is true. In this 'dA specification, the Del content rate means that the component (B) is weighed at 1.01r#, and 40
Component (B) non-bath material after placing it in a cage made of zero-mesh stainless steel wire mesh, immersing it in 100 g of toluene, leaving it at 5°C for 24 hours, pulling out the cage, and air-drying it at room temperature. Measure the cape) and then follow the formula below [
It is calculated and refers to the ratio value.

[(BJE insoluble matter weight t)/llX100(%)
-Cm (If the del content of the plow component exceeds 70%, the environmental stress cracking resistance of the resin composition of the present invention becomes low (unpreferably).

There are no particular restrictions on the polymerization method for component (B) of the present invention, but production by emulsion polymerization is industrially most advantageous, and any known technology related to emulsion polymerization can be applied. In the present invention, 100 parts by weight of component (A) and 1 to 1 part of component (B)
However, if the content of component (B) is less than 1 part by weight, the effect of improving the environmentally stressed pillars is insufficient. If the temperature increases, not only the effect will be reduced, but also the rigidity will be greatly reduced, which is not preferable.

In order to mix component (4) and component (B) in the present invention, a known mixing technique is applied to mix the components (4) and (B) in an emulsified state, a particulate state,
Alternatively, the desired mixture can be easily obtained by blending both components in a molten state and melt-kneading.In the following cases, the component (B) is produced by an emulsion polymerization method, and the polymerized latex is It can be blended with the N component in an emulsified, particulate or MPTA state and melt-kneaded through a dehydration process or at the same time as the dehydration process. mixer,
There are mix routers, conitors, extruders, rolls, etc. It is also possible to apply the t-expansion method disclosed in Japanese Unexamined Patent Publication No. 56-131656.

Furthermore, in the present invention, it is also possible to add additives other than those mentioned above, such as pigments, dyes, stabilizers, dispersants, reinforcing materials, fillers, and erasing agents.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples and Reference Examples, but the present invention is not limited to these Examples.

Note that the parts and parts in each example are based on pan weight.

Reference Example 1 (A) Preparation of Component (1) A-1, A-2, A-3, A-5 In the presence of the rubber latex shown in Table 1, add this to the corresponding unit, Manufactured by emulsion polymerization method.

(2) A-4 A toluene solution of EPDM dem was added at a ratio of ik as shown in Table 1, and produced by a solution polymerization method.

(3) A-6, A-7, A-8 Expanded reference column 21 by the emulsion polymerization method of the ratio polymer shown in Table 1.
B) Preparation of ingredients
While continuously adding 100 parts of the monomer mixture shown in Table 2,
It was manufactured by emulsion polymerization at a temperature of 70"C.

Table 3 shows the properties of the obtained component (B).

In addition, the abbreviations of the long chain bifunctional polymers used in Table 2 are as follows.

0(CI(2CE(20)2-C-C=CH2CH.

CH3 o(cH2ca, o) 5-cc=cH.

9. Each physical property value is determined by the following method.

(1) Glass transition temperature (BJ component lux ya-Calcicum falconide obtained by pouring it into aqueous solution 7), drying the solid, and thermal analysis using a 910 differential scanning calorimeter (a DuPont type measuring instrument) and a 990 I measured the height using a meter.

(2) Solubility parameter value of each polymer used for calculation of solubility parameter in each column [unit: (can/cc) 31
/J is as follows.

Gtylated polyacrylate; 8.8 Ethyl polyacrylate; 9.4 Polymethyl methacrylate; 9.5 Polyacrylonitrile; 12.5 Polystyrene; 9.1 (3) Del content (B) component latex with calcium monide Dry the solid obtained by pouring it into the aqueous solution. The 1.0.9 was pounded, processed as described above in 5, measured, and calculated in 2).

Actual Tsi Example 1 and Comparative Example 1 Table 1 (A-1) 80 parts of latex (as polymer) and Table 2 (B) 20 parts of component latex (as polymer)
were mixed in a latex state, and after pressurizing an aqueous calcium chloride solution, the resulting precipitate was filtered to recover the polymer.The resulting mixture was dried. After that, 4 parts of the nucleus crystal compound, 60 parts of t!!1(A-6) powder, 4.4'-isopropylidene-bis[monophenyl-
Sea-alkyl (CH~Czs) phosphite] [ADEKA ARGUS CHEMICAL (a)l! , Mar / (MARJC
) 1500 J (hereinafter abbreviated as stabilizer) in a Henkel mixer and fed to VC-40 (bent multi-screw extruder) manufactured by Chuo Kikai Seisakusho Co., Ltd. to obtain pellets. .

A molded article was prepared using the obtained T-pellet and the physical properties #fI were obtained.
The results are shown in Table 4, experiment numbers 1 to 24.

In addition, the physical property measurement 111 of each row was determined by the following method.90(1) Tensile yield point --- ASTM D-63
8(2) Izot impact strength...ASTM
D-256 (3) Chemical resistance (El environmental stress resistant column)
AsruD-658 Type I Dungeon (200cm) was fixed to a jig with 90 degrees of tension applied to it, coated with ethylene glycol monoethyl ether, and left at a temperature of 23°C. It is expressed as: 〉600 in the table is 300
(4) Layer peelability Using a 5-ounce injection molding machine, mold a 50x20x211 plate-shaped product with a date of 5x5x1. In Mugiki Sei 71 Example 6 and Comparative Example 6 (experiment numbers 64 to 44), the resin temperature was 240'O.

In other Examples and Comparative Examples, the resin temperature was 200℃, the injection speed was 9Qts/sec, and the mold temperature was 40℃. Evaluate your friend. ABtX A rank and B
Indicates a position in the middle of the ranks.

A: No peeling at all B: Slight peeling C: Significant peeling Numbers 1 to 18 are examples, and numbers 19 to 24 are comparative examples. As is clear from the comparative examples, when the glass transition temperature, gel content, and solubility parameters of component (B) deviate from the range of the present invention, the environmental stress resistance is poor, and the long-chain difunctional monomer is If the amount used is insufficient, the occurrence of delamination phenomenon will be observed.

Example 2 and Comparative Example 2 In Example 1, Table 2 (B-3) was used as the (B) component,
Pellets were obtained in the same manner as in Example 1, except that the mixing ratio of (A-1) and CB-5) and the blending ratio of (A-6) powder were changed as shown in Table 5. . A molded article was prepared from the obtained pellets, and the physical properties were evaluated, and the results are shown in Table 5.

As is clear from Table 5, if the amount of component (B) added is insufficient, the product will have poor environmental stress resistance, and if it is too much, it will be inferior to Warichu and cannot be put to practical use.

Example 6 and Comparative Example 6 Table 1 (A-1) Latex (B) component latex,
Table 1 The calcium chloride water was mixed with (A-7) latex or CA-8) latex in a latex state, and after pressurizing the liquid, it was stirred at 105 to 120"C.The obtained precipitate was filtered. After collecting and drying the polymerized mixture, the amount of t used in Example 1 was added to 100 parts of the mixture.
V manufactured by Chuo Kikai Seisakusho Co., Ltd. contains 0.6 parts of stabilizer.
C-4Q was fed to obtain pellets.

Use the obtained pellets to create molded products and examine their physical properties! ? P
One song was performed and the results are shown in Table 6.

It is clear from the 6th 7″l: As shown in the matrix resin (A
-7) or (A-8), the resin's I? [
Due to its high viscosity and high shear stress during injection molding,
When using tBl fraction that does not copolymerize long-chain difunctional monomers, a significant delamination phenomenon is observed (Experiment Nos. 40 to 42 in Table 6). However, with component (B) of the present invention, little or no separation phenomenon was observed, demonstrating the effects of the present invention (Experiment Nos. 64 to 69 in Table 6).

Example 4 and Comparative Example 4 ff 1 f A) component powder was mixed with Table 2 (B-3) 8 parts of latex (as a polymer) and 0.6 parts of stabilizer in a Henschel mixer, and then T manufactured by Toshiba Machine Co., Ltd. ? !
M-50 (co-rotating twin-screw kneading extruder) was fed to obtain pellets. A molded product was made from the obtained pellet and an evaluation was performed, and the results are shown in Table 7.

It can be seen that the effects of the present invention are exhibited regardless of the type of AJ acid component rubber.

Reference Example 3 (B) Preparation of Component 11k12o parts and 2 parts of sodium P deklebenzene sulfonate were placed in an autoclave, and heated while stirring.
The temperature was raised to 5°C. Next^, ferrous sulfate heptahydrate 0.0
05 parts, 0.01 part of ethylenecyamine, 0.01 part of sodium formaldehyde sulfoxylate, 0.6 part of Int.

Part [i? ! Add the dissolved aqueous solution.

Furthermore, 20% of a monomer mixture consisting of 70 parts of n-detel acrylate, 30 parts of methyl methacrylate, 1.00 parts of HD, and 0.5 parts of ethylene glycol dimethacrylate.
was poured into an autoclave, and 2.5 parts of potassium persulfate 0.2% aqueous ffj was added to initiate polymerization.

Simultaneously with the start of polymerization, the remaining amount of the monomer mixture was continuously added over 4 hours. At the same time as the start of t1 polymerization, a water bath solution prepared by dissolving 0.05 part of potassium persulfate in 20 parts of pure water was added to 6
Continuous addition over time. Too much! After the potassium Mate water bath solution is heated, the contents of the autoclave are cooled and the polymerization is closed.

The properties of the obtained acrylic acid ester polymer 8-25 were as follows: glass transition temperature -18°C, Del content 0.16%.

Although B-25 has the same monomer composition as B-20, the Del content is significantly different. That is,
The gel content of the acrylic ester polymer, which is one of the essential requirements of the present invention, is not uniquely determined by the m class and/or the amount of soot added to the polyfunctional monofilament.

Example 5 Composition pellets were prepared using B-25 in the same manner as in Example 1, and the physical properties were evaluated. As a result, the tensile yield point was 410.
kg/c, *”, Izotsu impact strength 28kg C
m/(m, chemical resistance>600 minutes, layered <chick aA
and satisfies the purpose of the present invention.

〔Effect of the invention〕

As explained above, the thermoplastic resin composition of the present invention is
The molded product exhibits a layered peeling phenomenon, and exhibits an excellent effect in making the column resistant to environmental stress.

Patent applicant Denki Kagaku Kogyo Co., Ltd. October 8, 1985 Director of the Patent Office Michibe Uga 1, Indication of the case 1985 Patent Application No. 199575 2, Name of the invention Thermoplastic resin composition 3, Amendment Relationship with the case involving a person who makes a patent application Address of the patent applicant ■100 1-4-1 Yurakucho, Chiyoda-ku, Tokyo Column 5 of the detailed explanation of the invention in the specification, Contents of amendment (1), page 16, line 19 of the specification Correct the word ``dobiage'' for the eyes as ``andogaage''.

(2) "Methyl methacrylate" in Table 2 on page 26 of the specification is corrected to "methyl methacrylate."

Claims (1)

[Scope of Claims] 1. Including (A) a rubber-containing styrenic resin and (B) a copolymer, the (B) based on 100 parts by weight of the component (A)
In a thermoplastic resin composition containing 1 to 50 parts by weight of the component, the copolymer of component (B) is an acrylic ester monomer, or an acrylic ester monomer and another copolymerizable monomer. 100 parts by weight of the mixture with the following general formula I
: ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [In the formula, R^1 and R^2 are H or CH_3 groups, and X is -(
CH_2)_l(CHR^3)_m(CR^4R^5)
_n- group (l, m, and n are each an integer of 0 or more, and l+m+n is an integer of 5 or more, R^3, R^4, and R^5 are an alkyl group, an aryl group, an alkoxyl group, or a hydroxyl group) is a group) and/or ▲ There is a mathematical formula, chemical formula, table, etc. ▼ Group (x and y are each an integer of 0 or more, R^6 and R^
7 is H or CH_3 group, Y is -O-, -S-, -
SO_2-, -CH_2-, alkylidene group, or alkylene group) is obtained by copolymerizing 0.01 to 10 parts by weight of a long chain bifunctional monomer, and the solubility parameter is 8. 4-9.8 (cal/cc)^
1^/^2, a glass transition temperature of 20°C or less, and a gel content of 70% by weight or less.