JPH06107967A - Thermosetting type anti-fogging agent composition for light tool of automobile and light tool of automobil - Google Patents

Abstract

PURPOSE:To obtain an anti-fogging agent composition suitable as light tools of automobile by improving anti-fogging properties and adhesivity in a high- temperature environment. CONSTITUTION:A thermosetting type anti-fogging agent composition for light tool of automobile comprises a block or a graft copolymer which consists of a hydrophilic polymer part composed of N-methylol(meth)acrylamide, a given (meth)acrylamide-based compound and a (meth)acrylic acid lower alkyl and a hydrophobic polymer part composed of a vinyl type monomer containing a functional group such as sulfonic group or carboxyl group and a copolymerizable (meth)acrylic acid lower alkyl and has the weight ratio of the hydrophilic polymer part and the hydrophobic polymer part of 50/50 to 95/5. The hydrophilic polymer part may be mixed with a (meth)acrylic acid lower alkoxyalkylene glycol and the anti-fogging composition may contain a surfactant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-curable antifogging composition for a vehicle lamp mounted on an automobile or the like and a vehicle lamp. More specifically, the heat-curable antifogging composition and the heat-curable antifogging composition applied to the inner surface of a plastic lens or the like in a vehicle lamp that is exposed to a high temperature environment of 60 to 140 ° C. during use. The present invention relates to a vehicle lighting device obtained by coating an object.

[0002]

The present inventors have proposed the following antifogging agent as a method for imparting antifogging property to various transparent plastic materials (JP-A-2-255854). That is,
The first is an antifogging agent composed of a block or graft copolymer composed of a hydrophilic polymer portion and a hydrophobic polymer portion and a surfactant. The second is composed of a hydrophobic polymer portion and a hydrophilic polymer portion formed from an acrylamide derivative,
It is an antifogging agent containing a self-crosslinking block or graft copolymer and a surfactant. Thirdly, it comprises a hydrophobic polymer part, an acrylamide derivative and a hydrophilic polymer part formed from hydroxyalkyl (meth) acrylate, and contains a self-crosslinking block copolymer and a surfactant. It is an antifogging agent for polyester.

On the other hand, with respect to antifogging of vehicle lamps, even under high temperature environment when the lamp is used, that is, at a temperature of 60 to 140 ° C., the antifogging property, the appearance of the lens of the lamp, the coating strength and the adhesion are extremely long. It is required that the basic performance be maintained at 4 points.

[0004]

However, in the case of an antifogging agent comprising a block or graft copolymer having a specific composition having a self-crosslinking property and a surfactant according to the present inventors, an ordinary temperature range is used. The appearance, antifogging property, adhesiveness, and coating film strength in an environment of −20 to 60 ° C. are maintained for an extremely long time. However, in a high temperature environment, that is, 60 to 140
At the temperature of ° C, the antifogging coating film has a problem that its antifogging property and adhesiveness decrease with time. Therefore, even under such a high temperature environment as in a normal environment, the appearance, the adhesion, the antifogging property and the coating film strength which can be practically used can be maintained for a long period of time. Development was strongly demanded.

The present invention has been made by paying attention to the problems of the prior art as described above, and the purpose thereof is particularly 60-
By improving the anti-fogging property and the adhesiveness under a high temperature environment of 140 ° C., the vehicle lighting device can be used in an actual usage environment of −20 to −20.
At 140 ° C., a heat-curable antifogging agent composition for vehicle lighting, which can exhibit excellent antifogging property, adhesion, coating film strength and coating film appearance for a long time, and this antifogging agent composition were applied. To provide a vehicle lamp.

[0006]

In order to achieve the above object, the present inventors have proposed the above antifogging coating film proposed by the present inventors under the high temperature environment of 60 to 140 ° C. The cause of the deterioration of the adhesiveness and adhesion was examined. As a result, when the coating film is placed in a high temperature environment of 60 to 140 ° C., the crosslinking reaction of the antifogging coating film progresses, the crosslinking density increases with time, and the penetration of water into the coating film. Since it was lower than in the initial period, the antifogging property was lowered over time.

On the other hand, the adhesion was lowered because internal stress was accumulated in the coating film due to the progress of the crosslinking reaction with time and the coating film could not follow the expansion of the substrate. The factors that promote the crosslinking reaction of this coating film were the following two points. That is, the first point is that hydrophilic monomers having a hydroxyl group that form the hydrophilic polymer portion of the block or graft copolymer react with each other. The second point is that the glycidyl group, N-methylol group, which constitutes the hydrophilic polymer portion,
N-methylol ether group, carboxyl group, glycidyl group, N-methylol group, N-methylol ether group, which constitutes a hydrophobic polymer portion with a vinyl-type monomer having any one of cross-linking functional groups, an acid anhydride group, A coating film which is practically usable as a crosslinking reaction with a vinyl-type monomer having a crosslinking functional group of either a carboxyl group or an acid anhydride group does not react with all the crosslinking functional groups during the formation of an antifogging coating film. A cross-linking reaction that develops strength occurs, and the unreacted cross-linking functional group further reacts in a high temperature environment of 60 to 140 ° C.

The inventors of the present invention have made use of the previously proposed technique to eliminate the above-mentioned two factors that reduce the antifogging property and the adhesiveness in a high temperature environment, and to improve the crosslink density, block or graft of the coating film. As a result of extensive studies on adjustment of hydrophilicity and hydrophobicity of the copolymer, the present invention has been completed.

That is, the heat-curable antifogging agent composition for vehicle lighting according to the first aspect of the present invention is represented by 1 to 15% by weight of N-methylol (meth) acrylamide, represented by the general formula 1 or 2. 35 to 86% by weight of at least one N-substituted or unsubstituted (meth) acrylamide compound
And 1 to 30% by weight of a vinyl-type monomer having a hydrophilic polymer portion formed by 15 to 50% by weight of at least one kind of lower alkyl (meth) acrylate and a sulfonic acid group, a carboxyl group or a phosphoric acid group. And a hydrophobic polymer portion formed from 70 to 99% by weight of a lower alkyl (meth) acrylate having a copolymerizability with the vinyl monomer, the hydrophilic polymer portion and the hydrophobic polymer portion. The block or graft copolymer has a weight ratio of 50/50 to 95/5.

In the heat curable antifogging agent composition for vehicle lighting of the second invention, the hydrophilic polymer portion of the block or graft copolymer is 1 to 15 parts by weight of N-methylol (meth) acrylamide. %, The general formula 1 or 2
20 to 79% by weight of at least one N-substituted or unsubstituted (meth) acrylamide compound represented by: and at least one or more lower alkyl (meth) acrylate 15
To 50% by weight and at least one or more lower alkoxyalkylene glycol (meth) acrylates represented by the following general formula 3 are contained in an amount of 5 to 50% by weight.

Further, the heat-curable antifogging agent composition for vehicle lighting according to the third invention comprises a heat-curable antifogging agent composition for vehicle lighting according to the first or second invention, and a surfactant incorporated therein. The mixing ratio of the block or graft copolymer and the surfactant is 100: 0.5 to 30 in terms of solid content weight ratio. A vehicle lamp according to a fourth aspect of the present invention is a vehicle lamp according to any one of the first to third aspects, wherein the heat-curable antifogging agent composition for a vehicle lamp is applied to a base material,
It is characterized in that it is heat-cured at a temperature of 45 ° C. to form an antifogging coating film on the surface.

Next, the present invention will be described in detail in order. First, the block or graft copolymer in the present invention will be described. The hydrophilic polymer portion of the block or graft copolymer is composed of 1 to 15% by weight of N-methylol (meth) acrylamide, an N-substituted or unsubstituted (meth) acrylamide compound represented by Chemical Formula 1 or Chemical Formula 2 above. 35 to 86% by weight of at least one or more, 15 to 50% by weight of at least one lower alkyl (meth) acrylate, or 1 to 15% by weight of N-methylol (meth) acrylamide, the above Chemical Formula 1 or Chemical Formula 2 N represented by
20 to 79% by weight of at least one or more substituted or unsubstituted (meth) acrylamide compounds, 15 to 50% by weight of at least one lower alkyl (meth) acrylate, and lower (meth) acrylic acid represented by Chemical Formula 3 above. It is composed of 5 to 50% by weight of at least one kind of alkoxyalkylene glycol.

In order to maintain the adhesiveness between the coating film and the substrate exhibiting the antifogging property in the high temperature environment of the temperature range of 60 to 140 ° C. for a long period of time and to develop the practical coating film strength, a single amount is required. It is necessary to use N-methylol (meth) acrylamide as the body. Further, the crosslinking density can be adjusted to an optimum value depending on the abundance, and the abundance is 1 to 1
It is 5% by weight. If it is less than 1% by weight, the cross-linking density of the coating film is insufficient and sufficient coating film strength cannot be obtained. On the other hand, 1
When it exceeds 5% by weight, the crosslink density becomes too high and the antifogging property is lowered, and further, the adhesiveness to the base material is lowered at the initial stage and in a high temperature environment of 60 to 140 ° C.

Further, in the hydrophilic polymer portion, the monomers constituting the hydrophilic polymer portion are N-methylol (meth) acrylamide and the N-substituted or unsubstituted (meth) acrylamide group represented by the above chemical formula 1 or chemical formula 2. In the case of a system consisting of at least one compound and at least one lower alkyl (meth) acrylate, at least one or more N-substituted or unsubstituted (meth) acrylamide compounds 35 to 86
It is composed by weight percent. On the other hand, N-methylol (meta)
Acrylamide, at least one or more N-substituted or unsubstituted (meth) acrylamide compound represented by the above Chemical Formula 1 or Chemical Formula 2, at least one or more lower alkyl (meth) acrylate, and lower (meth) acrylic acid In the case of a component system composed of at least one kind of alkoxyalkylene glycol, it is composed of 20 to 79% by weight of at least one kind of N-substituted or unsubstituted (meth) acrylamide compound.

In particular, by comprising at least one monomer of the above chemical formula 1 or an unsubstituted (meth) acrylamide compound, excellent antifogging at the initial stage of the coating film and in a high temperature environment of 60 to 140 ° C. Sex is maintained for a long time. In each of the component systems, when the amount of this monomer is less than 35% by weight or 20% by weight, the antifogging property in the initial and high temperature environments is deteriorated. On the other hand, 86 wt% or 79 wt%
If it exceeds, the penetrating force of water into the coating film becomes too strong, and the coating film strength decreases.

Examples of the N-substituted or unsubstituted (meth) acrylamide compound represented by the above Chemical Formula 1 or Chemical Formula 2 are (meth) acrylamide, N-methyl (meth) acrylamide, and N, N'-dimethyl (meth). ) Acrylamide, N-ethyl (meth) acrylamide, N, N'-diethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth )
Acrylamide, diacetone (meth) acrylamide,
N- (meth) acryloyl piperidine, N- (meth) acryloyl morpholine, etc. can be used. These monomers and any of the monomers described below can be obtained as commercial products, and those synthesized according to known methods can also be used.

Further, the hydrophilic polymer portion is the first or second
In any of the inventions (1) to (6), it was not conventionally compounded in order to secure the antifogging property in a high temperature environment.
It is necessary to blend at least one kind of lower alkyl acrylate, and the content thereof is in the range of 15 to 50% by weight. When the amount of this monomer is less than 15% by weight, the strength of the coating film is insufficient at the initial stage or in a high temperature environment of 60 to 140 ° C. On the other hand, if it exceeds 50% by weight, the lower alkyl (meth) acrylate is hydrophobic and the hydrophilicity of the coating film is lowered, so that the antifogging property in the initial or high temperature environment is lowered.

Examples of the lower alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth) acrylic. Acid n-
Butyl, i-butyl (meth) acrylate, t-butyl (meth) acrylate and the like can be used.

The hydrophilic polymer portion contains 5 to 50% by weight of at least one kind of lower alkoxyalkylene glycol (meth) acrylate in the second invention. This monomer is slightly less hydrophilic than N-substituted or non-substituted (meth) acrylamide compounds and less hydrophobic than lower alkyl (meth) acrylate, and therefore has a higher hydrophilicity. It is used for the purpose of adjusting the hydrophilicity and hydrophobicity of the polymer and for suppressing the reactivity with the N-methylol group because the hydroxyl group is blocked by the alkyl group.

That is, when the proportion of the N-substituted or unsubstituted (meth) acrylamide compound in the monomer constituting the hydrophilic polymer portion is high, a part of this monomer is (meth) acrylic acid lower By substituting the alkoxyalkylene glycol, it is possible to improve the antifogging property without significantly reducing the coating film strength in the initial and high temperature environments. When the blending ratio of this monomer is less than 5% by weight, the antifogging property of the coating film is insufficient, and when it exceeds 50% by weight,
Coating strength is insufficient.

As the lower alkoxyalkylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate (where n is preferably an integer of 1 to 10), ethoxyethylene glycol (meth) acrylate ( Here, n is preferably an integer of 1 to 10), methoxypropylene glycol (meth) acrylate (here, n is preferably an integer of 1 to 10) and the like can be used.

Next, the hydrophobic polymer portion of the block or graft copolymer will be described. The hydrophobic polymer portion is composed of 1 to 30% by weight of a monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group and 70 to 99% by weight of a lower alkyl (meth) acrylate having a copolymerizability therewith. Composed. When the amount of the monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group is less than 1% by weight, the transparency of the coating film is lowered, and when it exceeds 30% by weight, the adhesion between the coating film and the substrate is lowered. Further, this monomer also functions as an acid catalyst during the cross-linking reaction of N-methylol (meth) acrylamide in the hydrophilic polymer portion. The cross-linking reaction mainly occurring in the present invention is a cross-linking reaction between N-methylol (meth) acrylamides.

Examples of this monomer include (meth) acrylic acid-3-sulfopropyl and (meth) acrylic acid-2.
-Sulfoethyl, 2-acrylamido-2-methylpropanesulfonic acid, (meth) acrylic acid, crotonic acid, itaconic acid, itaconic acid half ester, maleic acid half ester, maleic acid, mono (2- (meth) acryloyloxyethyl) Acid phosphate and the like can be used.

The copolymerizable lower alkyl (meth) acrylate is a lower alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 4 carbon atoms. When the blending ratio of this monomer is less than 70% by weight, the adhesion between the coating film and the base material is lowered, and when it exceeds 99% by weight, the transparency of the coating film is lowered. As the monomer, the above-mentioned lower alkyl (meth) acrylate is used.

Next, the weight ratio of the hydrophilic polymer portion to the hydrophobic polymer portion in the block or graft copolymer needs to be 50/50 to 95/5. When the proportion of the hydrophilic polymer portion is less than 50% by weight, the hydrophilicity of the block or graft copolymer is lowered, and the interaction between the block or graft copolymer and the surfactant is weakened, so that the initial Not only the anti-fog property but also the anti-fog persistence decreases. On the other hand, when the proportion of the hydrophobic polymer portion is less than 5% by weight, the strength of the coating film and the adhesion to the substrate are impaired.

The block or graft copolymer comprising a hydrophilic polymer portion and a hydrophobic polymer portion of the present invention can be synthesized by a conventionally known method, but particularly, it is easy to industrially produce and has a wide range of performance. From this standpoint, those produced by a radical polymerization method using a polymeric peroxide, a polyazo compound, or a radical copolymerization peroxide as a polymerization initiator are preferable. In this case, as the radical polymerization initiator used, a conventionally known compound having two or more peroxy bonds or azo bonds in one molecule is used, and a compound having a radical copolymerizable group and a peroxy bond in one molecule is used. As the polymerization method, a usual bulk polymerization method, suspension polymerization method, solution polymerization method, emulsion polymerization method or the like is adopted.

Next, as a typical production example of the block copolymer of the present invention, a polymerization method using a polymeric peroxide as a polymerization initiator will be described below. First, by polymerizing a monomer that forms a hydrophilic polymer portion using a polymeric peroxide, a peroxy bond-containing hydrophilic polymer having a peroxy bond introduced into the chain is obtained. When a monomer that forms a hydrophobic polymer portion is added to this and polymerization is performed, the peroxy bond in the hydrophilic polymer chain is cleaved to efficiently obtain a block copolymer.

A typical production example of the graft copolymer of the present invention will be described using a radical copolymerizable group-containing peroxide as a polymerization initiator. First, by containing a peroxy bond by copolymerizing a vinyl-type monomer that forms a hydrophilic polymer with an ordinary free radical polymerization initiator under the condition that the peroxy bond of the radical copolymerizable group-containing peroxide is not cleaved. A hydrophilic copolymer is obtained. Next, under the condition that this peroxy bond is cleaved, a vinyl-type monomer that forms a hydrophobic polymer is added to this, and polymerization is carried out, so that the peroxy bond in the hydrophilic polymer is cleaved and grafted efficiently. A copolymer is obtained. The block or graft copolymer thus synthesized can freely control the molecular weights of the hydrophilic polymer portion and the hydrophobic polymer portion.

Next, in the heat-curable antifogging composition of the third invention, a surfactant is added. This surfactant is generally used, and one or more kinds of surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants and zwitterionic surfactants. It is an agent. Among these, nonionic surfactants or anionic surfactants are preferable from the viewpoint of the sustainability of the effect, and in particular, the combination of polyoxyethylene alkylaryl ethers and dialkylsulfosuccinates has a long antifogging property. It is suitable from the standpoint of preventing the change in the appearance and the appearance of the coating film.

Examples of nonionic surfactants include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether and polyoxyethylene oleyl ether, polyoxyethylene octylphenol, polyoxyethylene nonylphenol and the like. Polyoxyethylene alkylaryl ethers, polyoxyethylene acyl esters such as polyoxyethylene glycol monostearate, polypropylene glycol ethylene oxide adducts, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate Oxyethylene sorbitan fatty acid esters, alkyl phosphates, polyoxyethylene alkyl ether phosphates Phosphoric acid esters such as Le, sugar esters, cellulose ethers are used.

Examples of the anionic surfactant include fatty acid salts such as sodium oleate and potassium oleate, higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and sodium alkylnaphthalenesulfonate. Alkylbenzene sulfonates and alkylnaphthalene sulfonates, naphthalene sulfonic acid formalin condensates, dialkyl sulfosuccinates, dialkyl phosphate salts, polyoxyethylene sulfate salts such as sodium polyoxyethylene alkylphenyl ether sulfate, and the like are used.

Examples of the cationic surfactant include amine salts such as ethanolamines, laurylamine acetate, triethanolamine monoformate, stearamidoethyldiethylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and diamine. Lauryl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride,
Quaternary ammonium salts such as lauryl dimethyl benzyl ammonium chloride and stearyl dimethyl benzyl ammonium chloride are used.

Examples of the zwitterionic surfactant include fatty acid type amphoteric surfactants such as dimethylalkyllauryl betaine and dimethylalkylstearyl betaine, sulfonic acid type amphoteric surfactants such as dimethylalkylsulfobetaine, and alkylglycine. used.

The mixing ratio of these surfactants is a solid content weight ratio, and the block or graft copolymer: surfactant = 1.
00: 0.5 to 30. The blending amount of the surfactant is 0.
If the amount is less than 5 parts by weight, long-term antifogging property cannot be obtained, and if the amount is more than 30 parts by weight, the water resistance and the strength of the coating film are lowered.

The block or graft copolymer and the surfactant may be mixed by dissolving or dispersing the block or graft copolymer in an organic solvent or a mixed solvent of water and an organic solvent or water. A surfactant may be added therein, or the surfactant may be added together with the monomer forming the block or graft copolymer.

As the solvent used in this case, alcohols such as water, methanol, ethanol, n-propanol, isopropanol, n-butanol and diacetone alcohol, methyl cellosolve, ethyl cellosolve,
Butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, and other alcohol ether solvents, methyl ethyl ketone, methyl isobutyl ketone, and other ketone solvents, methyl acetate, ethyl acetate, butyl acetate, and other ester solvents, benzene, toluene, xylene And the like, and amide solvents such as formamide and dimethylformamide. Of these, alcohol solvents, alcohol ether solvents, and mixed solvents thereof are particularly preferable.

In the heat-curable antifogging agent composition of the present invention, various conventional additives such as an ultraviolet absorber, a leveling agent, a curing catalyst and an antioxidant can be blended if necessary.

Next, the antifogging processing of a vehicle lamp using the heat-curable antifogging agent composition for a vehicle lamp of the present invention will be described. That is, 70 to 145 is applied to the inner surface of the plastic lens of the lamp by applying an ordinary paint.
A coating film is formed by heat curing at a temperature of ° C. As the plastic lens, a lens made of polycarbonate, polymethylmethacrylate, or the like is used.
Due to this anti-fog processing, the vehicle lighting incorporating a plastic lens with anti-fog property under actual use environment,
Not only the appearance and adhesion of the coating film, but also the antifogging property and the coating film strength can be maintained for an extremely long time.

The coating environment has a relative humidity of 60%.
R. H. The following is preferable. This is because the antifogging agent composition of the present invention is very hydrophilic and tends to absorb water. That is, relative humidity 60% R.
H. When the coating is applied in an environment exceeding 10 ° C., the coating film tends to whiten after heat curing and the appearance tends to deteriorate. In order to suppress this whitening tendency, it is effective to partially use a solvent having a low evaporation rate and a low evaporation rate of water when the solvent is volatilized.

As the coating means, the coating means for ordinary paints, that is, the roll coating method, the spraying method, the dipping method, the brush coating method, the spin coating method, the flow coating method and the like are applied.

[0041]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. The number of copies is based on weight. (Reference Examples 1 to 15) (Synthesis of Block Copolymer) A block copolymer was synthesized as follows by two-step polymerization using a polymeric peroxide represented by the following chemical formula 4 as a polymerization initiator. The polymerization conditions shown below are such that the charged monomers are almost completely removed at each stage in both the first-stage polymerization for forming the hydrophilic polymer portion and the second-stage polymerization for forming the hydrophobic polymer portion. It is a condition for polymerizing.

[0042]

Embedded image - _{[CO (CH 2) 4 COO (} C 2 H 4 O) 3
CO (CH ₂ ) ₄ COOO] ₁₀ -Methyl Cellosolve 100 in a reactor equipped with a thermometer, stirrer and reflux condenser.
Part, and heated to 70 ° C. while blowing nitrogen gas, and methylcellosolve A part Polymeric peroxide B part shown by Chemical formula 4 N-methylol (meth) acrylamide C part Compound D part shown by Chemical formula 1 or Chemical formula 2 (Meth) acrylic acid lower alkyl E part A mixed solution consisting of the compound F part represented by Chemical formula 3 was charged over 2 hours, and the polymerization reaction was further carried out for 2 hours (first stage polymerization). Thereafter, a mixed solution comprising methyl cellosolve G part, vinyl type monomer having a sulfonic acid group, a carboxyl group, or a phosphoric acid group, H part, and lower alkyl (meth) acrylate, I part, was added over 30 minutes, and the mixture was heated at 75 ° C. The polymerization reaction was carried out for 5 hours. Tables 1 to 3 show the number of parts A to I and the polymerization results. (Reference Examples 16 to 27) (Synthesis of Graft Copolymer) A graft copolymer was synthesized using t-butylperoxymethacryloyloxyethyl carbonate. The polymerization conditions shown below are the first to form the hydrophilic polymer portion.
It is a condition under which the charged monomers are almost completely polymerized in each stage of stage polymerization and second stage polymerization for forming a hydrophobic polymer.

First, 100 parts of methyl cellosolve was charged into the reactor used in Reference Example 1, heated to 85 ° C. while blowing nitrogen gas, and 33.6 parts of methyl cellosolve t-butylperoxyoctanoate 4. 0 part t-butylperoxymethacryloyloxyethyl carbonate 2.4 parts N-methylol (meth) acrylamide C part Compound represented by Chemical Formula 1 or Chemical Formula 2 D part (meth) acrylic acid lower alkyl E portion Compound represented by Chemical Formula 4 The mixed solution consisting of Part F was charged over 2 hours, and the polymerization reaction was further performed for 7 hours (first stage polymerization). After that, 110
After heating to ℃, a mixture containing methyl cellosolve G part vinyl type monomer having sulfonic acid group, carboxyl group, or phosphoric acid group H part (meth) acrylic acid lower alkyl I part is charged over 30 minutes, A polymerization reaction was carried out at 110 ° C. for 7 hours. Tables 4 and 5 show the number of parts of C to I and the polymerization results. Reference Examples 28 to 30 (Synthesis of Random Copolymer) Methylcellosolve 10 was added to the reactor used in the synthesis of Reference Example 1.
0 part was charged and heated to 85 ° C. while blowing nitrogen gas, and methyl cellosolve 36 parts t-butylperoxyoctanoate 4 parts N-methylol (meth) acrylamide C part Compound D shown in Chemical formula 1 or Chemical formula 2 Part Lower alkyl (meth) acrylate E Part Compound represented by Chemical formula G Part Vinyl type monomer having sulfonic acid group, carboxyl group or phosphoric acid group H part Lower alkyl (meth) acrylate I part Liquid mixture Was charged over 2 hours, and a polymerization reaction was further performed for 9 hours. Table 6 shows the number of copies of C to I and the polymerization results.
It was shown to.

The abbreviations in Tables 1 to 6 have the following meanings. N-MAAm: N-methylol acrylamide DMAAm: N, N-dimethyl acrylamide ACMO: N-acryloylmorpholine MMA: methyl methacrylate IBMA: i-butyl methacrylate M20G: methoxydiethylene glycol methacrylate M40G: methoxytetraethylene glycol methacrylate AA: Acrylic acid MAA: Methacrylic acid SEM: 2-Sulfoethyl methacrylate MC: Methyl cellosolve Further, the solid content in the column of the polymerization result represents% by weight. The viscosity represents the viscosity (poise, P) of the polymerization solution at 25 ° C. The ratio of the hydrophilic polymer represents the ratio (%) of the polymer synthesized in the first stage polymerization to the total amount of the polymer.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

[Table 5]

[0050]

[Table 6]

(Examples 1 to 20 and Comparative Examples 1 to 13) For vehicle lamps, the polymers synthesized in Reference Examples 1 to 30 were all diluted with methyl cellosolve so that the solid content of the polymer was 20% by weight. A heat-curable antifogging agent composition for vehicle lighting was obtained by blending the heat-curable antifogging agent composition and a diluted polymer solution with a surfactant. The compounding composition is shown in Tables 7-9.
Next, each composition was applied to a substrate using a bar coater in an environment having a relative humidity of 60% or less so that the dry film thickness was 5 μm, and heat-cured under each condition. Table 7
Abbreviations in 9 represent the following meanings.

Surfactant (a): Polyoxyethylene nonylphenyl ether, trade name Nonion NS-212 manufactured by NOF CORPORATION (b): Polyoxyethylene octylphenyl ether,
Nippon Oil & Fat Co., Ltd. product name Nonion HS-210 (c): Sodium n-dodecylbenzene sulfonate, Nippon Oil & Fat Co., Ltd. product name Newlex R (d): Dioctyl sulfosuccinate sodium, Nippon Oil & Fat Co., Ltd. product name Lapizole B80 (e): Octadecyl trimethyl ammonium chloride, trade name Cation AB (f): Dimethyl alkyl palm betaine, manufactured by NOF Corporation trade name Anon BF substrate PC: Polycarbonate, PMMA: Polymethylmethacrylate curing Condition (1): 80 ° C for 60 minutes, (2): 120 ° C for 30 minutes, (3): 14
10 minutes at 0 ° C

[0053]

[Table 7]

[0054]

[Table 8]

[0055]

[Table 9]

The physical properties of each of the coating films thus obtained were evaluated by the following evaluation methods. The results are shown in Tables 10-14. (1) Adhesiveness A cross-cut cellophane tape peeling test according to JIS D0202 was performed. That is, 100 cross-cuts were made on the surface of the coating film with a cutter knife so as to reach the base material, cellophane adhesive tape (manufactured by Nichiban Co., Ltd.) was attached, peeled in the direction perpendicular to the adhesive surface, and the cross-cuts left without peeling off. The number of is represented by the following symbols. (a): 100/100, (b): 30/100, (c): 1
5/100, (d): 0/100 (2) Strength of coating film The change in appearance of the coating film left in each environment was visually evaluated.

◯: No change in appearance, ×: Change in appearance (3) Breath test The coating film left under each environment was placed in a thermostatic chamber at 20 ° C.
The coating film was blown and the cloudiness was visually determined.

⊚: No fog at all, ∘: Water droplets wet and spread instantly, Δ: Some fog is seen, ×: All over the surface (4) 60 ° C. steam test Coating in a thermostatic chamber at 20 ° C. Expose the membrane to warm steam at 60 ° C,
The time to start clouding was measured. In addition, Tables 10-14
In, “≧ 5” means that it is 5 hours or more,
"Immediately after" means that it will soon become cloudy.

Next, the environmental conditions of the test pieces used in the above respective tests are shown below. (A) Initial stage: Physical properties of coating film immediately after heating and drying (B) Moisture resistance: Coating film at 50 ° C. and relative humidity of 98% R.V. H.
Physical properties of coating film after standing in the environment for 300 hours (C) Thermal cycle resistance: coating film at 120 ° C. for 15.5 hours, room temperature for 30 minutes, −30 ° C. for 7.5 hours, room temperature for 3 hours
The condition of leaving each for 0 minutes as one cycle is 10
Physical properties of coating film after cycling (D) Heat resistance: 120 ° C when the base material is polycarbonate
If the base material is poly (methyl methacrylate) at 90 ° C, 1
Table 10 shows the evaluation results in each environment from (A) to (D) of coating film properties after being left for 000 hours.
Shown in 14.

[0060]

[Table 10]

[0061]

[Table 11]

[0062]

[Table 12]

[0063]

[Table 13]

[0064]

[Table 14]

As shown in Tables 1 to 14 above, the hydrophilic polymer portion of the block or graft copolymer does not include a portion formed of a monomer within a predetermined range (Comparative Examples 1, 3). ~ 8) and the weight ratio of the hydrophilic polymer portion and the hydrophobic polymer portion is not within a predetermined range (Comparative Example 2,
9) is inferior in either antifogging property, adhesiveness or coating strength.
Moreover, what used the random copolymer (Comparative example 10
No. 12) has extremely poor antifogging property and adhesion. In addition, when the surfactant is blended in a larger amount than a predetermined amount (Comparative Example 13), the coating film strength is deteriorated.

On the other hand, the heat-curable antifogging agent composition of each Example has excellent initial antifogging property,
The physical properties do not change even when left in an environment of 1000C for 90 hours. Note that it is found that the antifogging property is maintained for a long period of time by using a surfactant together, and that a combination of polyoxyethylene alkylaryl ethers and dialkylsulfosuccinate is particularly preferable (for example, Example 8,
(Comparison between 9, 14, 19, 20 and Examples 1, 17). (Examples 21 to 23) Next, the effect of relative humidity in the coating environment on the appearance of the coating film was tested. The composition of the antifogging agent composition used is shown in Table 15. The polymer used here was prepared by diluting Reference Example 9 having good results in the tests of Tables 10 to 14 with a mixed solvent of ethyl cellosolve having a slower evaporation rate than methyl cellosolve to a solid content of 20%, and then using a surfactant. Was mixed to obtain a heat-curable antifogging agent composition for vehicle lighting. Table 1
5 in MC with methyl cellosolve and E with ethyl cellosolve
Represented by C.

[0067]

[Table 15]

(Examples 24 to 35) The antifogging agent compositions shown in Table 15 were treated at a relative humidity of 45 to 80% R.V. H. Under the coating environment, the coating was applied so that the dry film thickness was 5 μm, and the change in the appearance of the coating film was evaluated by the haze value before and after the coating. The evaluation results are shown in Table 16. The abbreviations described in the base material and curing conditions are the same as above.

The appearance of the coating film was evaluated according to the following criteria. ◎: Difference in haze value before and after coating is less than 0.5% ○: Difference in haze value before and after coating is 0.5% or more and less than 1.0% Δ: Difference in haze value before and after coating is 1. 0% or more and less than 1.5% x: Difference in haze value before and after coating is 1.5% or more

[0070]

[Table 16]

(Examples 36 to 39 and Comparative Examples 14 and 1)
5) Examples 8 and 1 in which the physical properties were good under the respective environments
4, 19, and 20 were actually coated on the inner surface of the lens of the automobile lamp by a spray method or a flow coating method under a relative humidity of 60% or less so that the dry film thickness was 5 μm,
It was heat-cured to form an anti-fog property developing layer. This anti-fog processed lens was incorporated into a lamp and attached to an actual automobile. Tables 17 and 18 show the coating conditions.

[0072]

[Table 17]

[0073]

[Table 18]

Examples 36 to 39, Comparative Examples 14 and 15
The lamp obtained in 1) was actually mounted on an automobile and tested for 6 months. During this period, the ambient temperature rose to 60-140. As a result, the lamps of Comparative Examples 14 and 15 which were not subjected to the anti-fogging process fogged, whereas the lamps of Examples 36 to 39 did not fog and the appearance of the coating film and the coating film Adhesion was not deteriorated.

Therefore, the heat-curable antifogging composition for vehicle lighting of the present invention is suitable for imparting the antifogging property to the inner surface of the lens of the vehicle lighting for an extremely long period of time.

[0076]

As described above in detail, the heat-curable antifogging agent composition for vehicle lighting according to the first to third aspects of the present invention is particularly preferably 60 to 14
By improving the antifogging property and the adhesion property in a high temperature environment of 0 ° C, the excellent antifogging property, the adhesion property, the coating film strength and the coating film appearance that are initially exhibited in the actual use environment of the vehicle lamp. Has an excellent effect that it is favorably maintained for an extremely long period of time. Further, according to the second invention, it is possible to easily adjust the hydrophilicity and the hydrophobicity and the crosslink density, and it is possible to improve the antifogging property without lowering the coating film strength.

According to the third aspect of the present invention, it is possible to achieve long-term antifogging sustainability and to maintain a good appearance of the coating film. Furthermore, the vehicle lighting device according to the fourth aspect of the present invention has the anti-fogging composition applied to the inner surface of the lamp lens, and is heat-cured at 70 to 145 ° C. to be anti-fogging-processed, which is sufficient for practical use. It has an excellent effect that the antifogging property which can be maintained is maintained for an extremely long period of time, and the appearance, adhesion and coating film strength of the formed antifogging coating film are also maintained.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 11, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

[0004]

However, in the case of an antifogging agent comprising a block or graft copolymer having a specific composition having a self-crosslinking property and a surfactant according to the present inventors, an ordinary temperature range is used. The appearance, antifogging property, adhesiveness, and coating film strength in an environment of −20 to less than 60 ° C. are maintained for an extremely long time. However, in a high temperature environment, ie 60 to 1
At a temperature of 40 ° C., the antifogging coating has a problem that its antifogging property and adhesiveness decrease with time. Therefore, even under such a high temperature environment as in a normal environment, the appearance, the adhesion, the antifogging property and the coating film strength which can be practically used can be maintained for a long period of time. Development was strongly demanded.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

In the heat curable antifogging agent composition for vehicle lighting of the second invention, the hydrophilic polymer portion of the block or graft copolymer is 1 to 15 parts by weight of N-methylol (meth) acrylamide. %, The general formula 1 or 2
20 to 79% by weight of at least one N-substituted or unsubstituted (meth) acrylamide compound represented by: and at least one or more lower alkyl (meth) acrylate 15
To 50% by weight and 5 to 50% by weight of at least one kind of lower alkoxyalkylene glycol (meth) acrylate represented by the general formula 3 above.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

Further, in the hydrophilic polymer portion, the monomers constituting the hydrophilic polymer portion are N-methylol (meth) acrylamide and the N-substituted or unsubstituted (meth) acrylamide group represented by the above chemical formula 1 or chemical formula 2. In the case of a component system consisting of at least one compound and at least one lower alkyl (meth) acrylate, at least one N-substituted or unsubstituted (meth) acrylamide compound 35
˜86% by weight. On the other hand, N-methylol (meth) acrylamide, at least one or more of the N-substituted or unsubstituted (meth) acrylamide compounds represented by Chemical Formula 1 or Chemical Formula 2, and at least one or more lower alkyl (meth) acrylate. And in the case of a component system consisting of at least one kind of (meth) acrylic acid lower alkoxyalkylene glycol represented by the above Chemical Formula 3, at least one or more N-substituted or unsubstituted (meth) acrylamide compound is from 20 to 79% by weight. Composed.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

In particular, by using at least one monomer of the N-substituted or unsubstituted (meth) acrylamide compound represented by Chemical Formula 1 or Chemical Formula 2, the initial temperature of the coating film and 60 to 140 ° C. The excellent antifogging property under high temperature environment is maintained for a long time. In each component system,
If the amount of this monomer is less than 35% by weight or 20% by weight, the antifogging property in the initial and high temperature environments is deteriorated. On the other hand, when it exceeds 86% by weight or 79% by weight, the penetrating power of water into the coating film becomes too strong and the coating film strength is lowered.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

Further, the hydrophilic polymer portion is the first or second
In any of the inventions, in order to secure adhesion and coating strength in a high temperature environment, it is necessary to blend at least one kind of lower alkyl (meth) acrylate that has not been conventionally blended. Content is 15 ~
It is in the range of 50% by weight. When the amount of this monomer is less than 15% by weight, the coating film strength under a high temperature environment of 60 to 140 ° C is insufficient. On the other hand, if it exceeds 50% by weight, the lower alkyl (meth) acrylate is hydrophobic and the hydrophilicity of the coating film is lowered, so that the antifogging property in the initial or high temperature environment is lowered.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0019

[Correction method] Change

[Correction content]

The hydrophilic polymer portion contains 5 to 50% by weight of at least one lower alkoxy alkylene glycol (meth) acrylate represented by Chemical Formula 3 in the second invention. This monomer is slightly less hydrophilic than the N-substituted or unsubstituted (meth) acrylamide compound represented by Chemical Formula 1 or Chemical Formula 2 and less hydrophobic than lower alkyl (meth) acrylate. Since it has characteristics, it is used for the purpose of adjusting the hydrophilicity and hydrophobicity of the hydrophilic polymer, and for the purpose of suppressing the reactivity with the N-methylol group because the hydroxyl group is blocked by the alkyl group. .

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

That is, when the ratio of the N-substituted or unsubstituted (meth) acrylamide compound represented by the above chemical formula 1 or 2 in the monomer constituting the hydrophilic polymer portion is high, this monomer is used. To improve the antifogging property without significantly lowering the coating film strength in the initial and high temperature environments by replacing a part of the above with the lower alkoxyalkylene glycol (meth) acrylate represented by the chemical formula 3 above. You can
If the mixing ratio of this monomer is less than 5% by weight, the antifogging property of the coating film is insufficient, and if it exceeds 50% by weight, the coating film strength is insufficient.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

Examples of the lower alkoxyalkylene glycol (meth) acrylate represented by the above chemical formula 3 include methoxyethylene glycol (meth) acrylate (here,
n is preferably an integer of 1 to 10), ethoxyethylene glycol (meth) acrylate (where n is 1 to 10)
Is preferable, and (meth) acrylic acid methoxypropylene glycol (where n is preferably an integer of 1 to 10) and the like can be used.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

Next, the hydrophobic polymer portion of the block or graft copolymer will be described. The hydrophobic polymer portion is composed of 1 to 30% by weight of a vinyl type monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group, and 70 to 99% by weight of a lower alkyl (meth) acrylate having a copolymerizability therewith. %. If the vinyl type monomer having a sulfonic acid group, a carboxyl group or a phosphoric acid group does not satisfy 1% by weight, the transparency of the coating film decreases, and if it exceeds 30% by weight, the adhesion between the coating film and the substrate decreases. To do. Further, this monomer also functions as an acid catalyst during the cross-linking reaction of N-methylol (meth) acrylamide in the hydrophilic polymer portion. The cross-linking reaction mainly occurring in this invention is N-
It is a cross-linking reaction between methylol (meth) acrylamides.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

As a coating means, a usual coating means such as a roll coating method, a spraying method, a dipping method, a brush coating method, a spin coating method, a flow coating method and a bar coater method is applied.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

The abbreviations in Tables 1 to 6 have the following meanings. N-MAAm: N-methylol acrylamide DMAAm: N, N'-dimethyl acrylamide ACMO: N-acryloylmorpholine MMA: methyl methacrylate IBMA: i-butyl methacrylate M20G: methoxydiethylene glycol methacrylate M40G: methoxytetraethylene glycol methacrylate AA : Acrylic acid MAA: Methacrylic acid SEM: 2-Sulfoethyl methacrylate MC: Methyl cellosolve Further, the solid content in the column of the polymerization result represents% by weight. The viscosity represents the viscosity (poise, P) of the polymerization solution at 25 ° C. The ratio of the hydrophilic polymer represents the ratio (%) of the polymer synthesized in the first stage polymerization to the total amount of the polymer.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

[0049]

[Table 5]

[Procedure Amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction content]

[0050]

[Table 6]

[Procedure Amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

(Examples 1 to 20 and Comparative Examples 1 to 13) For vehicle lamps, the polymers synthesized in Reference Examples 1 to 30 were all diluted with methyl cellosolve so that the solid content of the polymer was 20% by weight. A heat-curable antifogging agent composition for vehicle lighting was obtained by blending the heat-curable antifogging agent composition and a diluted polymer solution with a surfactant. The compounding composition is shown in Tables 7-9.
Then, each composition was treated with a relative humidity of 60% R.V. so that the dry film thickness was 5 μm. H. It was applied to a substrate using a bar coater under the following environment, and heat-cured under each condition. The abbreviations in Tables 7 to 9 have the following meanings.

[Procedure Amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

[0061]

[Table 11]

[Procedure Amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction content]

[0063]

[Table 13]

[Procedure Amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

(Examples 36 to 39 and Comparative Examples 14 and 1)
5) Examples 8 and 1 in which the physical properties were good under the respective environments
Nos. 4, 19, and 20 actually showed 60% relative humidity on the inner surface of the lens of the automobile lamp. H. It was applied by a spray method or a flow coating method under the following environment so that the dry film thickness was 5 μm, and was heat-cured to form an antifogging coating film. This anti-fog processed lens was incorporated into a lamp and attached to an actual automobile. Tables 17 and 18 show the coating conditions.

[Procedure 18]

[Document name to be amended] Statement

[Correction target item name] 0074

[Correction method] Change

[Correction content]

Examples 36 to 39, Comparative Examples 14 and 15
The lamp obtained in 1) was actually mounted on an automobile and tested for 6 months. During this period, the environmental temperature rose to 60 to 140 ° C. As a result, the lamps of Comparative Examples 14 and 15 which were not subjected to the anti-fogging process fogged, whereas the lamps of Examples 36 to 39 did not fog and the appearance of the coating film and the coating film Adhesion was not deteriorated.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication location C08F 293/00 MRC 7142-4J (72) Inventor Hiroshi Omura 5 Rokukanyama, Taketoyo-cho, Chita-gun, Aichi prefecture Chome 3

Claims (4)

[Claims] 1. N-methylol (meth) acrylamide 1 to 15% by weight, N represented by the following general formula 1 or 2
A hydrophilic polymer portion formed of at least one or more 35 to 86% by weight of a substituted or unsubstituted (meth) acrylamide compound and at least one or more 15 to 50% by weight of a lower alkyl (meth) acrylate, and a sulfonic acid. Base,
Vinyl type monomer 1 having carboxyl group or phosphoric acid group 1
To 30% by weight and a hydrophobic polymer portion formed from 70 to 99% by weight of a lower alkyl (meth) acrylate having copolymerizability with this vinyl type monomer, and the hydrophilic polymer portion and the hydrophobic polymer portion. The weight ratio of the functional polymer portion is 50/50 to
A heat-curable antifogging agent composition for vehicle lighting, comprising a block or graft copolymer of 95/5. ## STR00001 ## CH ₂ ═CR ₁ CONR ₂ R _{3 In the} above formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, R ₃ Represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an N, N-dimethylaminopropyl group. [Chemical 2] In the above formula, R ₁ is a hydrogen atom or a methyl group, and A is −
_{(CH 2) 4 -, -} (CH 2) 5 - or - (CH _{2) 2}
-O- (CH _{2) 2} - represents a. 2. The block or graft copolymer is
The hydrophilic polymer portion is 1 to 15% by weight of N-methylol (meth) acrylamide, and at least one or more N-substituted or unsubstituted (meth) acrylamide compounds represented by the general formula 1 or 2 79% by weight, (meta)
At least one kind of lower alkyl acrylate 15 to 5
The heating for a vehicle lamp according to claim 1, wherein the heating amount is 5 wt% to 50 wt% of at least one lower alkoxy alkylene glycol (meth) acrylate represented by the following general formula 3. Curable antifog composition. CH ₂ ═CR ₁ CO (OR ₂ ) n OR _{3 In the} above formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is an ethylene group or a propylene group, R ₃ is a methyl group or an ethyl group, and n is It represents an integer of 1 to 23. 3. A heat-curable antifogging agent composition for vehicle lighting according to claim 1 or 2, wherein a surfactant is blended, and the blending ratio of the block or graft copolymer and the surfactant is solid weight. The ratio is 100: 0.5 to 30. A heat-curable antifogging composition for vehicle lighting, which is characterized in that the ratio is 100: 0.5 to 30. 4. A heat-curable antifogging composition for vehicle lighting according to claim 1, 2, or 3 is applied to a base material, and 70 to 145 is coated.
A vehicular lamp which is heat-cured at a temperature of ℃ to form an anti-fog coating film on the surface.