JP2001049078A - Weatherproof resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a super weatherproof resin composition in which the degree of exhibition of each of hydrophobic function and UV stabilizing ability can be arbitrarily controlled according to the situation. SOLUTION: This resin composition contains two polymers (A) and (B), wherein the polymer (A) is prepared by polymerization of a monomer component containing p wt.% of a hydrophobic monomer and q wt.% of a UV resistant monomer and the polymer (B) is prepared by polymerization of a monomer component containing r wt.% of a hydrophobic monomer and s wt.% of a UV resistant monomer, and wherein p>r; and q<s.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitable for use in paints and other coatings.

[0002]

2. Description of the Related Art Hitherto, in the development of paints and various coating agents particularly requiring weather resistance of a coating film, research has been mainly made on the structure of a polymer constituting the paint resin and a crosslinking method. Particularly recently, a polymer in which a reactive compound having an ultraviolet light resistance function is directly incorporated into the resin skeleton in a hydrophobic resin having relatively good weather resistance has been developed as a super weather resistant resin, and a conventional weather resistant resin has been developed. (See, for example, Japanese Patent Application Laid-Open No. 5-25547.)

However, in the production process of the above-mentioned polymer, only a polymer having a fixed ratio of a group having a hydrophobic function and a group having an ultraviolet-resistance function directly incorporated into the resin skeleton can be obtained. Therefore, only a certain effect can be exhibited as the weather resistance effect. That is, there is a drawback that, for example, when a resin having a particularly high hydrophobicity function is required or a resin having a particularly high ultraviolet ray stabilizing ability is required depending on the use situation, it cannot be dealt with.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a resin composition having an ultra-weather resistance, which can freely set the degree of each function of hydrophobicity and ultraviolet light resistance according to the situation. To provide things.

[0005]

Means for Solving the Problems The present inventor has made intensive studies to solve the above problems. As a result, conventionally, a group having a hydrophobic function and a group having an ultraviolet light resistance function were directly incorporated into a resin skeleton, and therefore, in an actual manufacturing process, only those having a specific ratio of those groups were constant. In contrast, the present invention was able to exhibit only a certain degree of weather resistance because it could not be obtained, but in the present invention, even if the groups having the above two functions were not directly incorporated into a common resin skeleton, the blend was not obtained. It was conceived that if the composition is contained in the same resin composition in such a form, weather resistance equivalent to or higher than the conventional level can be exhibited. By taking the form of a blend, it is possible to mix polymers having different degrees of exertion of the hydrophobic function and the ultraviolet light resistance function in a blending ratio according to the situation to form a polymer composition. It has been found that a polymer composition capable of exhibiting various functions can be easily obtained.

That is, the resin composition according to the present invention comprises:
A resin composition containing two types of polymers (A) and (B), wherein the polymer (A) is composed of p weight% of a hydrophobic monomer and q weight% of a UV-resistant monomer. The polymer (B) is a polymer synthesized from a monomer containing r wt% of a hydrophobic monomer and s wt% of a UV-resistant monomer. And p> r and q <s.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The resin composition according to the present invention is a resin composition containing two kinds of polymers (A) and (B), wherein the polymer (A) comprises p wt% of a hydrophobic monomer, The polymer (B) is a polymer synthesized from a monomer containing q-weight% of an ultraviolet-resistant monomer, and the polymer (B) has r-weight% of a hydrophobic monomer and s-weight of an ultraviolet-resistant monomer. %, And is characterized by having a relationship of p> r and q <s.

Hereinafter, the polymers (A) and (B) will be described first. In addition, for convenience, the ratio of p, q, r, and s is hereinafter referred to as “monomer ratio”. The polymer (A) contains a hydrophobic monomer in a proportion of p% by weight in a monomer ratio, preferably 1 ≦ p ≦ 90, more preferably 25 ≦ p ≦ 90.
≦ 70. When the monomer ratio p% by weight of the hydrophobic monomer in the polymer (A) is less than 1% by weight, the hydrophilicity increases and water, which is a cause of resin deterioration, is easily taken in. Not preferred. On the other hand, when the content exceeds 90% by weight, the film becomes hard and brittle, and the film may not be able to be formed due to poor solubility in a solvent.

The hydrophobic monomer according to the present invention is preferably selected from cyclohexyl (meth) acrylate, t-butyl methacrylate, (meth) acrylate having a perfluoroalkyl group, and a silicon-containing radical polymerizable compound. At least one compound. Examples of the (meth) acrylate having a perfluoroalkyl group include, for example, trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 2,2,3,4,4 4-hexafluorobutyl (meth) acrylate, 3,3,4,4
5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl (meth) acrylate, 3,3
4,4,5,5,6,6,7,7,8,8,9,9,1
0,10,11,11,12,12,12-Heneicosafluorododecyl (meth) acrylate, 3,3,4
4,5,5,6,6,7,7,8,8,9,9,10,
10,10-heptadecafluorodecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,7,
8, 8, 9, 9, 10, 10, 11, 11, 12, 1
2,13,13,14,14,14-pentacosafluorotetradecyl (meth) acrylate, 3,3,4
4,5,5,6,6,7,7,8,8,8-tridecafluorobutyl (meth) acrylate and the like.

As the silicon-containing radically polymerizable compound, a polysiloxane having a polymerizable unsaturated group at a terminal is particularly preferable. Examples of the polysiloxane having a polymerizable unsaturated group at the terminal include the following compounds.

[0011]

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The polymer (A) contains q-weight% of a UV-resistant monomer in a monomer ratio.
≦ q ≦ 30, more preferably 0 ≦ q ≦ 15. When q = 0, it means that the polymer (A) contains no UV-resistant monomer, that is, the polymer (A) is a resin characterized by a hydrophobic function. It means there is.

When the monomer ratio q of the UV-resistant monomer in the polymer (A) is more than 30% by weight, it tends to aggregate or color when mixed with other resins. This is not preferred because Further, the relationship between p and q in the polymer (A) in the present invention is not particularly limited as long as the above-described conditions are satisfied.
p> q. That is, the polymer (A) is preferably a polymer characterized by a hydrophobic function. This is because the preferred form of the polymer (B) described later is characterized by an ultraviolet light resistance function, and is therefore more consistent with the technical concept of "blend of polymers exhibiting different functions" of the present invention.

The UV-resistant monomer in the present invention is preferably a UV-absorbing monomer or a UV-stable monomer, and particularly preferably a UV-stable monomer. The UV-absorbing monomer has radical polymerizability, and is UV-α-wave or UV-
The monomer is not particularly limited as long as it has a maximum molar extinction coefficient of 10,000 or more at an absorption wavelength corresponding to β-wave, but is preferably a monomer represented by the following general formulas (3) and / or (4). Body.

[0015]

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[0016]

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The ultraviolet absorbing monomer represented by the general formula (3) (hereinafter, referred to as ultraviolet absorbing monomer (3)) is
In the formula, a substituent represented by R ⁵ is a hydrogen atom or a carbon atom 1
And a substituent represented by R ⁶ is a linear or branched alkylene group having 1 to 6 carbon atoms, and a substituent represented by R ⁷ is a hydrogen atom or methyl. A substituent represented by X is a hydrogen atom,
Halogen group, C1-8 hydrocarbon group, C1-4
Are benzotriazoles composed of an alkoxy group, a cyano group or a nitro group.

As the above-mentioned ultraviolet absorbing monomer (3), specifically, for example, 2- [2'-hydroxy-5
'-(Methacryloyloxymethyl) phenyl] -2H
-Benzotriazole, 2- [2'-hydroxy-5 '
-(Methacryloyloxyethyl) phenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxypropyl) phenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-5'-
(Methacryloyloxyhexyl) phenyl] -2H-
Benzotriazole, 2- [2'-hydroxy-3'-
t-butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-t-butyl-3'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole , 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5- Methoxy-
2H-benzotriazole, 2- [2'-hydroxy-
5 '-(methacryloyloxyethyl) phenyl] -5
-Cyano-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -6-t-butyl-2H-benzotriazole,
Examples include 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, but are not particularly limited. Among these, an ultraviolet absorbing monomer in which at least one of R ⁵ and X is a hydrogen atom is preferable. One kind of these ultraviolet absorbing monomers (3) may be used alone, or two or more kinds thereof may be used as appropriate.

The UV-absorbing monomer represented by the general formula (4) (hereinafter referred to as UV-absorbing monomer (4))
Wherein the substituents represented by R ⁸ is constituted by a straight-chained or branched alkylene group having 2 to 3 carbon atoms, benzotriazoles configured substituent is hydrogen atom or a methyl group represented by R ⁹ It is. Specific examples of the ultraviolet absorbing monomer (4) include, for example, 2- [2′-hydroxy-5 ′-(β-methacryloyloxyethoxy) -3′-t-butylphenyl] -4 -T-butyl-
Examples include 2H-benzotriazole, but are not particularly limited. These UV absorbing monomers (4)
May be used alone, or two or more kinds may be appropriately mixed and used.

The UV-stable monomer that can be used in the present invention is not particularly limited as long as it has radical polymerizability and has a function of quenching when free radicals are generated. Is the following general formula (1)
And / or a monomer represented by (2).

[0021]

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[0022]

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The UV-stable monomer represented by the general formula (1) (hereinafter referred to as UV-stable monomer (1)) is
In the formula, the substituent represented by R ¹ is constituted by a hydrogen atom or a cyano group, and the substituents represented by R ² and R ³ are each independently constituted by a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms. , R ⁴ is a hydrogen atom or a carbon atom 1
And a substituent represented by Y is a piperidine group composed of an oxygen atom or an imino group. The substituent represented by R ² or R ³ is specifically, for example, a hydrogen atom, a methyl group, or an ethyl group, and the substituent represented by R ⁴ is specifically, for example,
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, A tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group and the like.

Specific examples of the ultraviolet-stable monomer (1) include, for example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine,
(Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-
1,2,2,6,6-pentamethylpiperidine, 4-
(Meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy- 2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,
Examples thereof include 2,6,6-tetramethylpiperidine, but are not particularly limited. As the ultraviolet light-stable monomer (1), only one kind may be used, or two or more kinds may be appropriately mixed and used.

The UV-stable monomer represented by the general formula (2) (hereinafter referred to as UV-stable monomer (2)) is
In the formula, the substituent represented by R ¹ is constituted by a hydrogen atom or a cyano group, and the substituents represented by R ² and R ³ are each independently constituted by a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms. , Y are piperidines comprising an oxygen atom or an imino group.

Specific examples of the above-mentioned UV-stable monomer (2) include, for example, 1- (meth) acryloyl-
4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4
-Cyano-4- (meth) acryloylamino-2,2,
6,6-tetramethylpiperidine, 1-crotonoyl-
Examples thereof include 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, but are not particularly limited. One kind of the UV-stable monomer (2) may be used alone, or two or more kinds thereof may be appropriately mixed and used.

The polymer (B) contains r wt% of a hydrophobic monomer in a monomer ratio, and preferably, 0 ≦ r
≦ 90, more preferably 0 ≦ r ≦ 40.
When r = 0, it means that no hydrophobic monomer is contained in the polymer (B), that is, the polymer (B) is
In particular, it means a resin characterized by an ultraviolet resistance function.

If the monomer ratio r% by weight of the hydrophobic monomer in the polymer (B) is more than 90% by weight, the film becomes hard and brittle and the solubility in a solvent becomes poor, so that the composition becomes poor. It is not preferable because the film cannot be formed. The polymer (B) contains s wt% of a UV-resistant monomer in a monomer ratio, preferably 0.1 ≦ s ≦ 30, more preferably 5 ≦ s ≦. 20.

When the monomer ratio s% by weight of the UV-resistant monomer in the polymer (B) is less than 0.1% by weight, its radical scavenging ability, UV absorbing ability and UV stabilizing ability are low. This is not preferred. On the other hand, if it exceeds 30% by weight, it is not preferable because it is likely to be agglomerated when mixed with another resin or to be liable to be colored.

The relationship between r and s in the polymer (B) in the present invention is not particularly limited as long as the above-mentioned condition is satisfied, but preferably, r <s. That is,
The polymer (B) is preferably a polymer having a feature of resistance to ultraviolet light. This is because the above-mentioned preferred form of the polymer (A) is characterized by its hydrophobic function, and is therefore more consistent with the technical concept of "blend of polymers exhibiting different functions" of the present invention.

The polymers (A) and (B) may contain other monomers in addition to the specific monomers described above, as long as the effects of the resin composition of the present invention are not impaired. Good. Specific examples of the other monomers include carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, and maleic anhydride; vinyl sulfonic acid, styrene Sulfonic acid group-containing unsaturated monomers such as sulfonic acid and sulfoethyl (meth) acrylate; 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3 -Acidic unsaturated monomers such as -chloropropyl acid phosphate and 2-methacryloyloxyethylphenylphosphoric acid; hydroxyethyl (meth) acrylate, hydroxypropyl (meth)
Acrylate, caprolactone-modified hydroxy (meth)
Acrylates (for example, Plaxel FM manufactured by Daicel Chemical Industries, Ltd.), hydroxyl-containing monomers such as mono (meth) acrylate of polyester diol obtained from phthalic acid and propylene glycol; methyl (meth) acrylate, ethyl (meth) Acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth)
Acrylate, t-butyl (meth) acrylate, 2-
(Meth) acrylic acid alkyl esters such as ethylhexyl (meth) acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate; epoxy group-containing unsaturated monomers such as glycidyl (meth) acrylate; (meth) acrylamide; Nitrogen-containing unsaturated monomers such as N'-dimethylaminoethyl (meth) acrylate, vinylpyridine, vinylimidazole; vinyl chloride;
Halogen-containing unsaturated monomers such as vinylidene chloride; aromatic unsaturated monomers such as styrene, α-methylsterene and vinyltoluene; vinyl esters such as vinyl acetate; vinyl ethers; unsaturated cyanide compounds such as (meth) acrylonitrile; However, there is no particular limitation.
As the other monomer, if necessary, only one type may be used, or two or more types may be appropriately mixed and used.

The polymerization method for synthesizing the above-mentioned polymers (A) and (B) is not particularly limited, and various conventionally known polymerization methods such as a solution polymerization method and a suspension polymerization method may be used. Can be adopted. Solvents that can be used in copolymerizing the monomer composition by employing the solution polymerization method include, for example, toluene, xylene, and other high-boiling aromatic solvents; ethyl acetate, butyl acetate, Examples thereof include ester solvents such as cellosolve acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, but are not particularly limited thereto. One of these solvents may be used alone, or two or more of them may be appropriately mixed and used. Further, the amount of the solvent used is not particularly limited. Further, when the monomer composition is copolymerized by employing a suspension polymerization method or the like, an emulsifier or a polymerization regulator can be used.

When the monomer composition is copolymerized, a polymerization initiator can be used. Examples of the polymerization initiator include, for example, 2,2′-azobis- (2-methylbutyronitrile), t-butylperoxy-2-ethylhexanoate, and 2,2′-azobisisobutyronitrile And ordinary radical polymerization initiators such as benzoyl peroxide, di-t-butyl peroxide and cumene hydroperoxide, but are not particularly limited. Further, the amount of the polymerization initiator used is not particularly limited. Further, if necessary, a reducing agent such as sodium formaldehyde sulfoxylate (Rongalit) can be used as a decomposition accelerator of the polymerization initiator.

The reaction temperature is not particularly limited, but is preferably in the range of room temperature to 200 ° C., more preferably 40 ° C. to 1 ° C.
A range of 40 ° C. is more preferred. The reaction time may be appropriately set according to the reaction temperature, the composition of the monomer composition to be used, the type of the polymerization initiator, and the like so that the polymerization reaction is completed. Next, the resin composition of the present invention will be described.

The resin composition according to the present invention is a resin composition containing the two types of polymers (A) and (B), wherein the polymer (A) is a hydrophobic monomer. Is a polymer synthesized from a monomer containing p weight% and q-weight% of an ultraviolet-resistant monomer. The polymer (B) is composed of r weight% of a hydrophobic monomer, It is a polymer synthesized from a monomer containing s weight% of a monomer, and has a relationship of p> r, preferably p> 10r, and q <s, preferably 10q <s.

The relationship of p> r and q <s indicates that the monomer ratio of the hydrophobic monomer in the polymer (A) is smaller than the monomer ratio of the hydrophobic monomer in the polymer (B). And that the monomer ratio of the UV-resistant monomer in the polymer (B) is higher than the monomer ratio of the UV-resistant monomer in the polymer (A). This is defined by the technical concept of "a blend of polymers exhibiting different functions" in the present invention.

The polymer (A) accounts for 10 to 9 of the total resin composition.
It is preferably contained in the range of 9% by weight, and the polymer (B) is preferably contained in the range of 1 to 90% by weight of the whole resin composition. The mixing ratio of the polymers (A) and (B) is such that the content of the UV-resistant monomer in 1000 g of the total resin solid component of the composition is 0.0017 to 0.
It is preferable that the compounding amount is 35 mol, preferably 0.003 to 0.1 mol, and more preferably 0.007 to 0.05 mol.

The total resin solid component of the composition is 1000 g.
It is preferable that the total amount (g) of the hydrophobic monomer component occupying therein is 10% or more, preferably 20% or more, and more preferably 30% or more. The higher the hydrophobic component, the lower the water absorption of the whole composition. The water absorption here means
It refers to the water absorption after 1 g of the entire composition dried at 100 ° C. for 20 hours is immersed in water for 1 hour.
The water absorption is preferably 5% or less, preferably 2% or less, more preferably 1% or less, and still more preferably 0.5% or less. On the other hand, the water absorption in the case of the solvent type is 1% or less, preferably 0.5% or less, more preferably 0.1% or less.
Below, it is more desirable to make it 0.01% or less.

The water absorption can be reduced by adjusting the amount of the resin having the hydrophobic skeleton. The difference between the optimal amount of water absorption between the solvent type and the aqueous system is that aqueous resins are soluble in water /
Alternatively, it originally has an aqueous solution substance necessary only for dispersion. In addition, since the amount of the resin in the hydrophobic skeleton is affected by the interfacial tension of the resin, an appropriate amount varies depending on each resin. That is, since the fluororesin and the silicone resin are extremely liable to appear on the surface interface, even if the amount is reduced to 0.1% of the whole, an effect may be obtained. About 5% of the acrylic resin having another hydrophobic skeleton is required because such an interfacial energy is not so strong. The higher the amount, the better the water absorption. However, in order to maintain the compatibility balance as a material, it is better to set the content to 80% or less for better compatibility with other mixtures and storage stability.

When the polymers (A) and (B) are incompatible, the polymers (A) and (B) can be made compatible by adding a compatibilizing agent. For example, this can be achieved by the presence of a third component having both a block compatible with the polymer (A) and a block compatible with the polymer (B). By adjusting the amount of the third component, the overall compatibilization can be adjusted.

The number average molecular weight of the polymer having an ultraviolet-resistant monomer used for blending in the present invention is preferably at least 1,000, more preferably at least 2,000, and even more preferably at least 3,000. When the number average molecular weight is lower than 1000, the polymer has a tendency to be hydrophilic, and moisture on the surface causes the UV-resistant monomer component to fall off. To prevent this drop-out, compatibility with other polymers and a number average molecular weight of 1,000 or more are required.

In the resin composition of the present invention, other than the above-mentioned polymers (A) and (B), if necessary, other polymers,
Flame retardant for improving design and visibility, zinc, aluminum phosphate, aromatic monobasic acid for imparting rust prevention,
Rust inhibitors such as aminocarboxylic acids, antibacterial agents such as silver-based, zeolite-based and quaternary ammonium salts-based and antifungal agents may be added to prevent film deterioration due to bacteria and mold. Additives such as a dispersing wetting agent, a curing accelerator, and a defoaming agent can be appropriately compounded within a range that does not impair the object of the present invention.

Examples of the other polymers include phenol resins; amino resins; urea resins, melamine resins,
Formaldehyde resins such as benzoguanamine resin and modified products thereof; crosslinked resins such as saturated polyester, unsaturated polyester, epoxy resin, diallyl phthalate resin (allyl resin), silicone, polyurethane and modified products thereof; polyethylene, polypropylene, polymethylpentene, Hydrocarbon plastics such as polybutene, crystalline polybutadiene, polystyrene, polybutadiene, styrene butadiene resin and modified products thereof; polyvinyl chloride, polyvinyl acetate, acrylic resin, polyvinylidene chloride, polytetrafluoroethylene, ethylene vinyl acetate copolymer , AS resin, ABS resin, ionomer, AAS resin, ACS resin and other polar vinyl plastics and their modified products; polyacetal, polyamide, polycarbonate, Engineering plastics such as phenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polysulfone, polyethersulfone, polyimide, polyamideimide, polyphenylene sulfide, and their modified products; cellulose-based materials such as cellulose acetate, cellulose acetate butyrate, celluloid, cellophane And plastics and their modifications.

In the composition according to the present invention, the polymer (A) and the polymer (B) to be blended each have a functional group derived from the specific monomer described above, and (A) and (B) Since the blending ratio of (1) can be freely set, the resin composition can exhibit various patterns of weather resistance levels depending on the situation. Hereinafter, specific examples of the blend form for obtaining the resin composition of the present invention will be described.

In the first blend mode, the polymer (A) is q
= 0, that is, when the polymer (B) contains a hydrophobic monomer unit but does not contain a UV-resistant monomer, and the polymer (B) has r =
0, that is, a case where a UV-resistant monomer unit is contained but a hydrophobic monomer is not contained. In this mode, the hydrophobic function and the ultraviolet light resistance function of the obtained polymer composition are imparted independently of the polymer (A) and the polymer (B), respectively. Various functional patterns can be exhibited depending on the mixing ratio of (B).

The second blend mode is a mode in which the polymer (A) or (B) used in the first mode is mixed with a conventional weather-resistant resin having hydrophobicity and ultraviolet light resistance. . For example, for a resin having a high hydrophobicity function and a low ultraviolet light resistance function (in this case, this becomes the polymer (A)), the resin contains an ultraviolet light resistant monomer unit but contains a hydrophobic monomer. When the polymer (B) is not added to enhance the UV resistance function, or on the other hand, for a resin having a high UV resistance function and a low hydrophobic function (in this case, this becomes the polymer (B)). In this case, the polymer (A) containing a hydrophobic monomer unit but not containing an ultraviolet-resistant monomer is added to enhance the hydrophobic function.

The third blend mode is a mode in which conventional weather-resistant resins having hydrophobicity and ultraviolet resistance and having different functions are blended. For example, a resin having a high hydrophobic function and a low UV resistance function (in this case, this is the polymer (A)) is a resin having a high UV resistance function and a low hydrophobic function (in this case, a polymer (A)). (B)
Is mixed to prepare a resin composition having both functions at the same level.

The present invention is applicable not only to the field of paints and other coating agents and films, but also to fields where various molding materials and plastic materials require weather resistance and light resistance.

[0049]

Hereinafter, specific examples of the present invention will be described.
The present invention is not limited to the following examples. In addition,
Polymers A and B used in the following Examples are the following Reference Examples 1 to
23. The number average molecular weights of the polymers A and B obtained in Reference Examples were analyzed by the following method. [Number average molecular weight] The number average molecular weight in terms of polystyrene was measured by gel permeation chromatography (GPC) under the following conditions.

Sample Preparation Using tetrahydrofuran as a solvent, polymer
05 g was dissolved in 1 g of tetrahydrofuran to prepare a sample. For those that do not dissolve, the increase in molecular weight due to crosslinking or the like is considered, but the measurement of the molecular weight was not possible. Apparatus A high-speed GPC apparatus HLC-8020 manufactured by Tosoh Corporation was used.

Column G3000H, G2000H and G manufactured by Tosoh Corporation
MHXL was used. Standard polystyrene TSK standard polystyrene manufactured by Tosoh Corporation was used. Measurement conditions Measurement was performed at a measurement temperature of 35 ° C. and a flow rate of 1 ml / min. [Reference Example 1 (Synthesis of Polymer A1)] 100 parts of butyl acetate was charged into a four-necked flask equipped with a stirrer, a thermometer, a cooler, a dropping funnel, and a nitrogen gas inlet tube, and the reflux temperature (12
(3-128 ° C.). While blowing nitrogen gas there, 0.5 part of methacrylic acid, 5 parts of methyl methacrylate, 25 parts of cyclohexyl acrylate, 29.5 parts of tert-butyl methacrylate, 20 parts of 2-ethylhexyl acrylate, 15 parts of hydroxyethyl methacrylate, and 5 parts of styrene , And 10% of a mixture consisting of 1.0 part of azobisisobutyronitrile was added all at once, and the remaining mixture was added dropwise from a dropping funnel over 4 hours, and then kept at 90 ° C. for 1 hour. Add 0.2 parts of azobisisobutyronitrile three times at 30 minute intervals,
After further maintaining at 90 ° C. for 2 hours, the solution was cooled to room temperature to obtain a solution of a polymer (hereinafter referred to as polymer A1). Table 1 shows the polymerization conditions, molecular weight, and the like. [Reference Examples 2 to 23 (Polymers A2 to A11, Polymers B1 to B1)
B7, comparative polymers CA1 to CA2, comparative polymers CB1
Synthesis of CB3)] The same operations as in Example 1 were carried out except that the composition and conditions of the polymerizable monomer in Reference Example 1 were as shown in Tables 1 to 3, to thereby obtain polymers A2 to A11 and polymer B1. ~
B7, comparative polymers CA1 to CA2, comparative polymers CB1
A solution of CB3 was obtained. The polymerization conditions, molecular weights, etc. are shown in Tables 1 to 3.

The polymer CB2 solution shows a yellow color, and its dried coating film also shows a yellow color (b * value> 5), and is a white, weather-resistant resin for clear use. Not suitable.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

Examples 1 to 11 <Evaluation in Clear> Polymers A1 to A11 and polymer B
Each of 1 to B7 was mixed at room temperature at a mixing ratio (weight ratio) of solid content as described in Table 4 to obtain a mixed solution. A polyfunctional isocyanate (Desmodur BL-3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was weighed with respect to these mixed liquids in such an amount that an equivalent ratio of isocyanate groups to hydroxyl groups in the mixed liquid was 1: 1. . Then, dibutyltin dilaurate was further added to the resin as a curing catalyst in an amount of 1: 1.
000 ppm was weighed and added.

On the other hand, the polymer A1 was blended with titanium oxide (Taipec CR-95, manufactured by Ishihara Sangyo Co., Ltd.) so that the concentration of the non-volatile pigment was 50% by weight, and was well dispersed in a sand mill. Curing agent (Sumidur N-320
0, manufactured by Sumitomo Bayer Urethane Co., Ltd.) in an amount such that the equivalent ratio of isocyanate groups to hydroxyl groups in the resin becomes 1: 1 and thinner (butyl acetate / ethyl acetate / xylene / toluene = 2 / (1/2/1) using an Iwata cup to dilute to 14 seconds, and spray-coated on a 0.8 mm thick aluminum plate to a thickness of 20 μm. After the coated white plate was left at room temperature for 20 minutes, it was cured for 1 hour in a dryer adjusted to 80 ° C. and returned to room temperature to prepare a white plate for clear evaluation.

Next, a clear mixture was applied to a white plate for evaluation with a bar coater to a thickness of 20 μm. After leaving at room temperature for 20 minutes, it was placed in a dryer adjusted to 200 ° C. for 30 seconds to advance curing. Thereafter, the temperature was returned to room temperature to obtain a plate for clear evaluation. Each plate for clear evaluation was evaluated for clearness according to the following weather resistance. Table 4 shows the results.

Weathering resistance: An accelerated weathering resistance test was performed using Sunshine Weather O-meter WEL-SUN-HC-B manufactured by Suga Test Instruments. The 60-degree gloss of the coating film was measured over time, and the time when the gloss retention relative to the initial gloss became 80% was measured. The operation method was based on JISK5400. As a comparison, for the UV-resistant monomer (UV-absorbing monomer and / or UV-stable monomer) present in all resins, an equimolar addition-type UV-resistant monomer was used as the corresponding polymer. The gloss retention was also evaluated in the same manner when added to A. At this time, the ultraviolet-absorbing monomer used for comparison was isooctyl-3- (3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenylpropionate, an ultraviolet-stable monomer. The body used was ADK STAB LA-52 manufactured by Asahi Denka Kogyo.

The criteria for the clear evaluation are as follows. A: Weather resistance can be maintained for 1,000 hours or more as compared with the case where the corresponding ultraviolet absorbing monomer and / or ultraviolet stable monomer is added to equimolar polymer A. ：: Weather resistance is maintained for 200 hours or more as compared with the case where the corresponding ultraviolet absorbing monomer and / or ultraviolet stable monomer is added to equimolar polymer A.

Δ: corresponding UV-absorbing monomer and / or
Or, the gloss retention rate does not change as compared with the case where the UV-stable monomer is added to the equimolar polymer A. X: 200 hours or more inferior to the case where the corresponding UV-absorbing monomer and / or UV-stable monomer was added to equimolar polymer A. <Evaluation with white paint> Titanium oxide (Taipec CR-95, manufactured by Ishihara Sangyo Co., Ltd.)
And a hardener (Sumidur N-3200, manufactured by Sumitomo Bayer Urethane Co., Ltd.)
Is weighed so that the equivalent ratio of isocyanate groups to hydroxyl groups in the resin becomes 1: 1 and thinner (butyl acetate / ethyl acetate / xylene / toluene = 2/1/2 /
In 1), dilute to 14 seconds with Iwata cup, 0.8
The aluminum plate was spray-coated to a thickness of 20 μm.
When the hydroxyl group value in the resin non-volatile component was 20 or less in hydroxyl value, the hydroxyl value was calculated as 20 and blended and painted. Finished white plate at room temperature for 20
After standing for a minute, the mixture was cured for 1 hour in a dryer adjusted to 80 ° C. and returned to room temperature to prepare a white paint evaluation plate.

Each of the white paint evaluation plates was evaluated according to the above-mentioned weather resistance. Table 4 shows the results. <Evaluation of water absorption> A mold having a length of 5 cm and a width of 5 cm was placed on a Teflon plate, and a mixture prepared by clear evaluation was poured so as to have a film thickness of 0.5 mm.
After putting in a dryer for 20 hours, the temperature was returned to room temperature to obtain a film for measuring the water absorption. The water absorption was evaluated by the following method. Table 4 shows the results.

Water absorption: Put the film in water at 60 ° C.
The water absorption after immersion for hours was measured. The criteria for evaluating the water absorption are as follows. ◎: 0.01% or less ○: 0.1 to 0.01% Δ: 0.5 to 0.1% ×: 1.0 to 0.5% XX: 1% or more

[0064]

[Table 4]

Comparative Examples 1-2 Polymers CA1-CA2
And Polymers B1 to B7 were mixed at room temperature at the mixing ratio (weight ratio) of solids as described in Table 4, and the same operation as in Examples 1 to 11 was performed. Paint evaluation and water absorption evaluation were performed. The results are shown in Table 4. Comparative Example 3 Comparative polymers CB1 and CB3 were mixed with polymers A1 to A11 in the same manner as in Examples 1 to 11 except that polymers B1 to B7 were used instead of polymers B1 to B7, and the physical properties of clear and white paints were evaluated. Was done. As a result, CB1 and CB3
There was hardly any difference in the use in the. On the other hand, in all of the examples, when compared with the mixed examples with B1 of Examples 1 to 11, although the water absorption did not change, the evaluation of the weather resistance was inferior by 200 hours or more. [Reference Example 24 (Production of polymer AB1)] 200 parts of butyl acetate was charged into a four-necked flask equipped with a stirrer, a thermometer, a cooler, a dropping funnel, and a nitrogen gas inlet tube, and was refluxed (123 to 128 ° C). Temperature. While blowing nitrogen gas there, 0.5 part of methacrylic acid, 20 parts of methyl methacrylate, 15 parts of cyclohexyl acrylate,
A mixture of 18 parts of tertiary butyl methacrylate, 20 parts of butyl acrylate, 15 parts of lauryl methacrylate and 1.0 part of azobisisobutyronitrile was mixed with 4 parts.
The solution was dropped from the dropping funnel over a period of time, and then kept at 90 ° C. for 0.5 hour. Thereafter, 0.2 part of azobisisobutyronitrile was added three times at 30 minute intervals, and further kept at 90 ° C. for 1 hour. Thereafter, while continuously blowing nitrogen gas there, 0.5 part of methacrylic acid, 65 parts of methyl methacrylate, ADK STAB LA-824 manufactured by Asahi Denka Kogyo Co., Ltd.
, 8.5 parts of tert-butyl methacrylate, 20 parts of butyl acrylate and 1.0 part of azobisisobutyronitrile were dropped from the dropping funnel over 4 hours, and then kept at 90 ° C for 0.5 hour. After that, 30
Three times at minute intervals, 0.2 parts of azobisisobutyronitrile was added, and the mixture was further kept at 90 ° C. for 1 hour, and then cooled to room temperature to obtain a polymer mixed solution (polymer AB1). [Examples 12 to 15 (Synthesis of mixed polymer in multi-stage polymerization, mixed system of various resin systems, use of multi-stage resin)
<Evaluation in Clear> Various polymer components and additives as needed are mixed at room temperature in the mixing ratio (weight ratio) shown in Table 5,
A mixture was obtained. A polyfunctional isocyanate (Desmodur BL-3175, manufactured by Sumitomo Bayer Urethane Co., Ltd.) was weighed with respect to these mixed liquids in such an amount that an equivalent ratio of isocyanate groups to hydroxyl groups in the mixed liquid was 1: 1. . Then, 1000 ppm of dibutyltin dilaurate was further weighed and added to the resin as a curing catalyst. On the other hand, the mixture prepared above was applied to a white plate for evaluation of clear prepared in Example 1 with a bar coater to a thickness of 20 μm. After leaving at room temperature for 20 minutes, it was placed in a dryer adjusted to 200 ° C. for 30 seconds to advance curing. Thereafter, the temperature was returned to room temperature to obtain a plate for clear evaluation.

Each of the clear evaluation plates was evaluated according to the following weather resistance. Table 5 shows the results. Weather resistance: An accelerated weather resistance test was performed using Sunshine Weather O-meter WEL-SUN-HC-B manufactured by Suga Test Instruments. The 60-degree gloss of the coating film was measured over time, and the time when the gloss retention relative to the initial gloss became 80% was measured. The operation method was based on JISK5400.
As a comparison, those prepared after removing all UV-resistant monomers (UV-absorbing monomers and / or UV-stable monomers) from all the mixtures were similarly evaluated as comparative mixtures.

The criteria for the clear evaluation are as follows. A: Weather resistance can be maintained for 1000 hours or more as compared with the evaluation result of the comparative mixture. ：: Weather resistance can be maintained for 200 hours or more as compared with the evaluation result of the comparative mixture. Δ: The gloss retention was unchanged as compared with the evaluation result of the comparative mixture. X: 200 hours or more inferior to the evaluation result of the comparative mixture. <Evaluation with white paint> The above mixed solution prepared with clear paint was treated with titanium oxide (Taipec CR-95, Ishihara Sangyo Co., Ltd.)
And a hardener (Sumidur N-3200, Sumitomo Bayer Urethane Co., Ltd.)
Was weighed so that the equivalent ratio of isocyanate groups to hydroxyl groups in the resin was 1: 1 and thinner (butyl acetate / ethyl acetate / xylene / toluene = 2/1/1).
2/1) Dilute to 14 seconds with Iwata Cup,
It was spray-coated to a thickness of 20 μm on a 0.8 mm thick aluminum plate. When the hydroxyl value of the resin was 30 or less in terms of hydroxyl value, the hydroxyl value was calculated as 30 and blended and painted. After leaving the completed white plate at room temperature for 20 minutes, it was cured for 1 hour in a dryer adjusted to 80 ° C. and returned to room temperature, to prepare a white paint evaluation plate.

Each of the white paint evaluation boards was evaluated for weather resistance. Table 5 shows the results. <Evaluation of Water Absorption> A mold having a length of 5 cm and a width of 5 cm was placed on a Teflon plate, and the above-mentioned mixture prepared with a clear paint was poured so as to have a thickness of 0.5 mm.
After placing in a dryer for 2 minutes, the temperature was returned to room temperature to obtain a film for measuring water absorption. The water absorption was evaluated by the following method.
Table 5 shows the results.

Water absorption: Put the film in water at 60 ° C.
The water absorption after immersion for hours was measured. The criteria for evaluating the water absorption are as follows. ◎: 0.01% or less ○: 0.1 to 0.01% Δ: 0.5 to 0.1% ×: 1.0 to 0.5% XX: 1% or more

[0070]

[Table 5]

Reference Example 25 (Production Example of Polymer A12 in Emulsion Polymerization) Pure water 6 was added to a flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser.
5 parts, 6.7 parts of 20% Aqualon HS-10 aqueous solution, 2
An emulsifier was charged with 3.3 parts of a 0% Aqualon RN-20 aqueous solution (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the temperature was raised to 75 ° C. with stirring while gently blowing nitrogen gas. After a while
One of the polymerizable monomer components consisting of 15 parts of 2-ethylhexyl acrylate, 1 part of glycidyl methacrylate, 1 part of acrylic acid, 1 part of 2-hydroxyethyl methacrylate, 15 parts of styrene, and 17 parts of t-butyl methacrylate
0% was dropped into the flask, and 3.3 parts of a 20% aqueous solution of Aqualon HS-10 was added to the remaining polymerizable monomer mixed component.
1.7 parts of an aqueous solution of Aqualon RN-20 (manufactured by Daiichi Kogyo Seiyaku) and 45 parts of pure water were added to obtain a pre-emulsion mixture. Subsequently, 0.6 part of a 5% aqueous solution of ammonium persulfate was added. After 10 minutes, the remaining pre-emulsion mixture and 2.4 parts of a 5% aqueous solution of potassium persulfate were uniformly added dropwise over 80 minutes. During dropping, keep the temperature between 75 ° C and 80
C., and after the addition was completed, the mixture was aged while stirring at the same temperature for 30 minutes. Next, 6.0 parts of 25% aqueous ammonia was added to neutralize the system in advance, followed by 15 parts of 2-ethylhexyl acrylate, 1 part of glycidyl methacrylate, 1 part of hydroxyethyl methacrylate, 15 parts of styrene,
To a polymerizable monomer component consisting of 18 parts of t-butyl methacrylate, 5 parts of an aqueous solution of 20% Aqualon HS-10,
2.5 parts of an aqueous solution of Aqualon RN-20 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), further added 65 parts of pure water, and 3.0 parts of a 5% aqueous solution of potassium persulfate and 2.0 parts of sodium hydrogen carbonate. 2.4 parts of 5% aqueous solution in 100
It was dripped evenly over minutes. During dropping, keep the temperature at 75 ° C
The temperature was kept at 80 ° C., and after the dropping was completed, the mixture was aged while stirring at the same temperature for 1 hour, and the solid content was 45% and the viscosity was 890 mPa · s.
(Polymer A12) was obtained. [Reference Example 26 (Production of Polymer AB5)] A flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser was charged with 67.0 parts of pure water, and stirred while gently blowing nitrogen gas. The temperature was raised to 70 ° C. below. Thereafter, 28.7 parts of cyclohexyl methacrylate, 20.8 parts of 2-ethylhexyl acrylate, and 0.9% of acrylic acid were added.
25% Aqualon HS in 5 parts polymerizable monomer component
4.0 parts of a -10 aqueous solution, 2.0 parts of a 25% aqueous solution of Aqualon RN-20 and 13.0 parts of pure water were added to obtain a pre-emulsion mixture 1. After 5% by weight of the mixture was added to the flask and the atmosphere was sufficiently replaced with nitrogen, 0.8 parts of a 5% aqueous solution of ammonium persulfate was added to initiate polymerization. After maintaining the inside of the reaction system at 70 ° C. for 10 minutes, the remaining pre-emulsion mixture 1 and 3.6 parts of a 5% aqueous solution of ammonium persulfate were uniformly dropped over 90 minutes. During the dropwise addition, the inside of the reaction system was kept at 70 ° C. After adding 3.5 parts of 5% aqueous ammonia and aging at 70 ° C. for 100 minutes, 16.0 parts of methyl methacrylate, 10 parts of 2-ethylhexyl acrylate, ADK STAB LA manufactured by Asahi Denka Kogyo Co., Ltd.
-82 4 parts, tertiary butyl methacrylate
25% Aqualon HS in 5 parts polymerizable monomer component
A pre-emulsion mixture 2 was obtained by adding 4.0 parts of a -10 aqueous solution, 2.0 parts of a 25% aqueous solution of AQUALON RN-20 and 13.0 parts of pure water. The pre-emulsion mixture 2 and 3.6 parts of a 5% aqueous solution of ammonium persulfate were uniformly dropped over 90 minutes. The temperature during the dropping was maintained at 70 ° C., and after the dropping was completed, the mixture was aged while stirring at the same temperature for 60 minutes, and then cooled to obtain an aqueous resin dispersion liquid (polymer AB5). [Examples 16 to 18 (Synthesis of mixed polymer by multistage polymerization in emulsion polymerization, preparation of mixed composition in emulsion system)] <Evaluation in clear> Polymer A, polymer in the ratio described in Table 6 B, other polymers and compounds at 45 ° C
Funnel, stirrer, nitrogen inlet tube, thermometer,
And a flask equipped with a reflux condenser to obtain a mixed composition. Using CS-12 manufactured by Chisso as a film-forming aid, a mixture for clear evaluation was obtained in addition to each resin so as to form a film at 0 ° C.

On the other hand, the prepared mixture was applied to the white plate for evaluation of clear prepared in Example 1 to a thickness of 20 μm using an applicator. After leaving it at room temperature for 20 minutes, place it in a dryer adjusted to 100 ° C.
After 0 minute, the film was formed. Thereafter, the temperature was returned to room temperature to obtain a plate for clear evaluation. Each was evaluated by the following weather resistance. Table 6 shows the results.

Weather resistance: A Daipla metal weather made by Daipla Wintes was operated under the following conditions, and a 60-degree gloss of the coating film was measured over time, and a time until the gloss retention with respect to the initial gloss became 80% was measured. did. The operating conditions were as follows: light intensity 80 W / cm ² , black panel temperature 80 ° C.
A cycle of light irradiation for 20 hours (relative humidity 50% other than during rainfall) to humidity for 4 hours (relative humidity 98%) was repeated, and rainfall was performed at a rate of 2 minutes during 60 minutes of light irradiation.

For comparison, a mixture prepared after removing all UV-resistant monomers (UV-absorbing monomers and / or UV-stable monomers) from the whole mixture was similarly evaluated as a comparative mixture. The criteria for clear evaluation are as follows. A: Weather resistance can be maintained for 400 hours or more as compared with the evaluation result of the comparative mixture.

：: Weather resistance can be maintained for 200 hours or more as compared with the evaluation result of the comparative mixture. Δ: The gloss retention was unchanged as compared with the evaluation result of the comparative mixture. X: 200 hours or more inferior to the evaluation result of the comparative mixture. <Evaluation with white paint> Titanium oxide (Taipec CR-9
5, using Ishihara Sangyo Co., Ltd.) Deionized water 66.67 Kao Demol EP 68.0 Emulgen 909 4.0 Ethylene glycol 24.0 HEC SP-600 3.0 Nopco 8034L 4.0 Titanium oxide Typpe CR95 400.0 Composition with a non-volatile pigment concentration of 75% by volume And dispersed well by a sand mill to obtain a pigment paste.
The mixed liquid prepared with the clear paint was added to the pigment paste, and sufficiently stirred with a disper to obtain a white paint for evaluation.
A 0.8 mm thick aluminum plate is coated with a white paint to a thickness of 20 μm by an applicator, and the white plate is left at room temperature for 20 minutes, cured in a dryer adjusted to 80 ° C. for 1 hour, returned to room temperature, and evaluated for white paint. Plate was prepared.

Each of the white paint evaluation plates was evaluated for weather resistance. Table 6 shows the results. <Evaluation of Water Absorption> A mold having a length of 5 cm and a width of 5 cm was placed on a Teflon plate, and the previously prepared mixed solution was poured so as to have a film thickness of 0.5 mm.
After a period of minutes, the temperature was returned to room temperature to obtain a film for measuring the water absorption. The water absorption was evaluated by the following method. Table 6 shows the results.

Water absorption: 1% by placing the film in water at 60 ° C.
The water absorption after immersion for hours was measured. The criteria for evaluating the water absorption are as follows. ◎: 0.5% or less ○: 0.5 to 2.0% △: 2.0 to 5.0% ×: 5.0 to 20% XX: 20% or more

[0078]

[Table 6]

[0079]

According to the present invention, there is provided a resin composition having super weather resistance, in which the degree of each of the hydrophobic function and the ultraviolet light stabilizing function can be freely set according to the situation. Can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 BG04W BG04X BG07W BG07X BG08W BG08X CP14W CP14X GH00 4J038 CG141 CG142 CG171 CG172 CH031 CH032 CH071 CH072 CH191 CH192 CH251 CH252 CL001 CL002 GA08 GA09 GA15 NA03

Claims (4)

[Claims] 1. A resin composition containing two types of polymers (A) and (B), wherein said polymer (A) contains p weight% of hydrophobic monomer, The polymer (B) is a polymer synthesized from a monomer containing q weight% of a monomer.
R weight% of hydrophobic monomer, s weight% of UV resistant monomer
Is a polymer synthesized from monomers containing p> r and q
A resin composition having a relationship of <s. 2. The resin composition according to claim 1, wherein q = 0 and / or r = 0. 3. The hydrophobic monomer is at least one selected from cyclohexyl (meth) acrylate, t-butyl methacrylate, (meth) acrylate having a perfluoroalkyl group, and a silicon-containing radical polymerizable compound. The resin composition according to any one of claims 1 and 2. 4. The ultraviolet-resistant monomer is a monomer represented by the following general formula (1) and / or (2):
The resin composition according to claim 1. Embedded image Embedded image