JPH06172676A - Uv-curable antifogging agent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent adhesivity, coating film strength and transparency and useful for plastic molding material, etc., by compounding respective specific block copolymer with photopolymerizable compound, polar solvent, photopolymerization initiator and surfactant at specifications. CONSTITUTION:The objective composition is composed of (A) a block copolymer consisting of (i) a hydrophilic polymer part composed of >=50wt.% of hydrophilic monomers such as (meth)acrylamide compound of formula I or formula II and hydroxyalkyl (meth)acrylate and (ii) a hydrophobic polymer part composed of hydrophobic monomers and containing 5-50wt.% of the part containing the structural unit of formula III at an (i)/(ii) weight ratio of 90/10 to 30/70, (B) a photopolymerizable compound of formula IV or formula V, (C) a polar solvent (e.g. methyl cellosolve) which is a good solvent of the component A, (D) a photopolymerization initiator such as benzoin and (E) a surfactant. The weight ratios of A/B/E are 100/(10-100)/(0.5-60) in terms of solid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-curable antifogging composition capable of imparting antifogging properties to various plastic molding materials, films, etc. and forming a coating film excellent in adhesion and strength. is there.

[0002]

2. Description of the Related Art Various plastic materials are used for applications such as underwater goggles, helmet shields, instrument covers, lenses, window glass of houses, window glass of vehicles, etc. by utilizing their transparency.

When the resin material used for these purposes is used in a place of high temperature and high humidity or in an environment where the temperature difference between both surfaces is large, water vapor is finely condensed on the surface of the resin material, resulting in fogging on the surface of the material. It has the drawback of occurring.

In order to solve this drawback, various antifog agents have been studied. The present inventors have so far proposed that a coating composition containing a heat-curable hydrophilic / hydrophobic block copolymer as a main component is useful as an antifogging agent for transparent resins (JP-A-2-255854). Gazette).
This heat-curable antifogging agent composition has a feature that satisfactorily imparts antifogging property, adhesion and coating film strength,
Since the heat treatment at a high temperature for a long time is required, the coating treatment speed cannot be said to be rapid, and it has been desired to speed up the coating treatment speed. In order to speed up such coating processing speed,
UV-curable antifog compositions are known.

However, the conventionally known ultraviolet-curing type antifogging composition is very excellent in productivity because it can form a cured coating film by irradiation with light for a short time, while it has an excellent antifogging property. There is a problem in that it is difficult to achieve a good balance of the three properties of coating property, coating film strength and adhesion.

In order to solve such problems, the present inventors have previously proposed a hydrophilic / hydrophobic block copolymer, a compound having two or more (meth) acryloyl groups, a fluorine-containing surfactant, a polar solvent and An ultraviolet curable antifogging composition comprising a photopolymerization initiator has been proposed (Japanese Patent Application No. 38742).

[0007]

However, this ultraviolet-curable type antifogging agent composition maintains the three characteristics of antifogging property, coating film strength and adhesiveness in a relatively well-balanced manner. The hydrophilic / hydrophobic block copolymer, which is one of them, does not have a crosslinkable functional group. Therefore, due to the fact that it does not chemically bond with other curing components, it has a drawback that the coating film whitens over time and the transparency is impaired, particularly in an environment of high humidity.

In addition, there is a problem that the strength of the coating film tends to decrease due to the moisture absorption of the coating film under such an environment. The present invention has been made by paying attention to the conventional problems as described above, and an object thereof is to impart excellent antifogging property to the surface of a transparent resin material, and to maintain the adhesiveness and the coating film strength. Another object of the present invention is to provide an ultraviolet-curable antifogging agent composition capable of maintaining good transparency even under a high humidity environment, maintaining appearance quality, and preventing a decrease in coating film strength.

[0009]

In order to achieve the above object, in the first invention of the present invention, the block copolymer shown as the component (A) and the (B) or (B ').
A photopolymerizable compound shown as a component, and a polar solvent (C) which is a good solvent for the hydrophilic polymer portion rather than for the hydrophobic polymer portion in the block copolymer (A),
Consisting of a photopolymerization initiator (D) and a surfactant (E),
Solid content weight ratio is (A) component / (B) or (B ') component /
Component (E) = 100/10 to 100 / 0.5 to 60.

A second invention is characterized in that, in the first invention, the block copolymer (A) is a block copolymer represented by the above (A '). Next, the present invention will be sequentially described in detail.

First, the block copolymer (A) component or (A ') component in the present invention will be described. The block copolymer (A) component or (A ′) component is composed of a hydrophilic polymer portion and a hydrophobic polymer portion, and the hydrophilic polymer portion (a) or (a ′) is one molecular chain. ) Has a function of being oriented on the surface side of the coating film when cured by ultraviolet rays and exhibiting excellent antifogging property.

Of these, in (a), since the hydrophilic polymer portion does not participate in the crosslinking reaction and can relatively freely move in the coating film, the orientation to the surface of the coating film during UV curing and Excellent antifogging effect. On the other hand, (a ')
In, the hydrophilic polymer portion is partially substituted by the general formula 3 having a radically polymerizable unsaturated bond, and when the antifogging agent composition is applied to a substrate and cured by ultraviolet rays, It has the effect of further improving the coating film strength.

These hydrophilic polymer moieties (a) or (a ') are represented by the general formula 1 or 2 in order to exhibit excellent antifogging properties and to maintain good coating strength. It is necessary to form at least 50% by weight of one or more monomers selected from N-substituted or unsubstituted (meth) acrylamide compounds and hydroxyalkyl (meth) acrylate. If the amount is less than 50% by weight, the antifogging performance tends to decrease.

Examples of these monomers include (meth)
Acrylamide, N-methyl (meth) acrylamide,
N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) Acrylamide, N- (meth) acryloylpiperidine, N- (meth) acryloylmorpholine,
Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and the like are used.

These hydrophilic polymer portions (a) or (a ') are other vinyl type monomers such as hydrophilic monomers other than the above, to the extent that the antifogging property and the coating strength are not impaired. A hydrophobic monomer or a vinyl type monomer having various functional groups may be used in combination. In particular, in (a ') of the hydrophilic polymer portion, in order to introduce the general formula 3, (meth) acrylic acid is copolymerized as described later to previously prepare the hydrophilic polymer portion (a'). ) And introducing a carboxyl group into the glycidyl (meth) acrylate and reacting it with the epoxy group in glycidyl (meth) acrylate, or conversely by copolymerizing glycidyl (meth) acrylate, the hydrophilic polymer part (a ') is preliminarily treated with an epoxy group. Any of the methods of introducing and reacting (meth) acrylic acid is utilized. Therefore, the hydrophilic polymer portion (a ′) is
It is necessary to use a part of either (meth) acrylic acid or glycidyl (meth) acrylate.

Next, the hydrophobic polymer portion (b), which is the other molecular chain of the block copolymer (A) component or (A ') component, has the antifogging composition applied to the substrate. When cured by ultraviolet rays, it has a function of causing a cross-linking reaction in the portion of the general formula 3 while orienting to the base material side to exert excellent coating film strength and adhesiveness.

As the hydrophobic vinyl type monomer forming the hydrophobic polymer portion (b), for example, methyl (meth) acrylate, ethyl (meth) acrylate, -n-propyl (meth) acrylate, Isopropyl (meth) acrylate, -n-butyl (meth) acrylate, isobutyl (meth) acrylate, -t-butyl (meth) acrylate,
2-Ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid esters such as stearyl (meth) acrylate, fragrances such as styrene, vinyltoluene, α-methylstyrene Group vinyl type monomer, vinyl formate, vinyl acetate,
Vinyl propionate, vinyl carboxylates such as vinyl stearate, butadiene, vinyl chloride, vinylidene chloride,
(Meth) acrylonitrile or the like is used.

Also in this hydrophobic polymer portion (b),
The general formula 3 is introduced in the same manner as for the hydrophilic polymer portion (a '). Therefore, the hydrophilic polymer portion (a ')
It is necessary to partially use either (meth) acrylic acid or glycidyl (meth) acrylate.
Furthermore, other vinyl-type monomers such as hydrophobic monomers other than the above, hydrophilic monomers and vinyl-type monomers having various functional groups can be used to the extent that the function as a hydrophobic polymer is not impaired. You may use together.

The block copolymer (A) in the present invention
Hydrophilic polymer part (a) in component or (A ') component
Alternatively, the weight ratio of (a ') to the hydrophobic polymer portion (b) is in the range of 90/10 to 30/70, 50/50 to 9
The range of 0/10 is preferable. If the hydrophilic polymer portion is less than 30% by weight, the antifogging property becomes insufficient, and if it exceeds 90% by weight, the coating film strength and the adhesiveness are impaired.

The introduction amount of the general formula 3 in the present invention is as follows: the hydrophobic polymer portion (b) of the block copolymer (A) component or the hydrophilic polymer portion (a ') of the component (A'). Alternatively, the proportion occupied in the hydrophobic polymer portion (b) must be in the range of 5 to 50% by weight. If this proportion is less than 5% by weight, the degree of cross-linking of the block copolymer will be insufficient, and it will be difficult to maintain transparency under high humidity and the coating strength will be insufficient. On the contrary, when it exceeds 50% by weight, the antifogging property and the adhesiveness are impaired.

Next, the block copolymer (A) of the present invention
A typical production example of the component or the component (A ') will be described below. The block copolymer (A) or (A ') component in the present invention is derived from a block copolymer containing a carboxyl group derived from (meth) acrylic acid by polymerization, or a glycidyl (meth) acrylate. To obtain one of block copolymers containing an epoxy group,
Subsequently, the general structural formula 3 is introduced by reacting glycidyl (meth) acrylate with respect to the former and (meth) acrylic acid with respect to the latter.

Among these, known methods are adopted as the method for producing the carboxyl group-containing block copolymer or the epoxy group-containing block copolymer, but particularly, the industrial productivity is easy and the performance is unclear. From this point of view, a radical polymerization method using a polymeric peroxide or a polyazo compound which is a compound having two or more peroxy bonds or azo bonds in one molecule as a polymerization initiator is preferably adopted. As the polymerization method, a usual bulk polymerization method, suspension polymerization method, solution polymerization method, emulsion polymerization method or the like is adopted.

As an example of using a polymeric peroxide among these polymerization methods, first, when a vinyl-type monomer forming a hydrophilic polymer portion is polymerized using a polymeric peroxide, a peroxy bond is introduced into the chain. A hydrophilic polymer containing a peroxy bond is obtained. When a monomer that forms a hydrophobic polymer portion is added to this and the polymerization is carried out, the peroxy bond in the hydrophilic polymer chain is cleaved to efficiently obtain a block copolymer. in this case,
On the contrary, first, the vinyl type monomer forming the hydrophobic polymer portion is polymerized to obtain a peroxy bond-containing hydrophobic polymer, and then the vinyl type monomer forming the hydrophilic polymer portion is added. It is also possible to obtain a block copolymer.

In the block copolymer thus obtained, the molecular weights of the hydrophilic polymer portion and the hydrophobic polymer portion can be freely adjusted. Further, the introduction amount of Chemical Formula 3 introduced into the hydrophobic polymer portion (b) or the hydrophilic polymer portion (a ′) is adjusted by the amount of (meth) acrylic acid or glycidyl (meth) acrylate to be copolymerized. be able to.

Next, reaction of the above-mentioned carboxyl group-containing block copolymer with glycidyl (meth) acrylate,
Alternatively, a method of introducing the chemical formula 3 by the reaction of the epoxy group-containing block copolymer and (meth) acrylic acid will be described.

As is known, the epoxy group has high reactivity,
When a tertiary amine or a quaternary ammonium salt is used as a catalyst, it reacts with a carboxyl group in a high yield to form a carboxylic acid ester. By utilizing this reaction, a carboxyl group-containing block copolymer Chemical formula 3 can be introduced into the middle or the epoxy group-containing block copolymer. That is, glycidyl (meth) acrylate is reacted into the carboxyl group-containing block copolymer, and (meth) acrylic acid is reacted into the epoxy group-containing block copolymer to introduce Chemical Formula 3.

As a catalyst in the reaction between the carboxyl group and the epoxy group, pyridine, isoquinoline, quinoline, N, N-dimethylcyclohexylamine, α-picoline, triethylamine, N-ethylmorpholine,
Amine such as N, N-dimethylaniline, amino alcohol such as N, N-dimethylethanolamine, N, N-diethylethanolamine, N-methyl-N, N-diethylethanolamine, N, N-dibutylethanolamine , Triethylbenzylammonium chloride, tetramethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, trimethylphenylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, tetra n-butylammonium bromide, N-benzyl A quaternary ammonium salt such as picolinium chloride is used.

In this reaction, hydroquinone, p-methoxyphenol, 4-hydroxy-, etc. are used for the purpose of suppressing the thermal polymerization of the chemical formula 3 introduced into the block copolymer.
It is preferable to add a small amount of a polymerization inhibitor such as 3-t-butylanisole or 4-t-butylcatechol, which is usually used for storing monomers.

Next, the photopolymerizable compound as the component (B) or (B ') will be described. The photopolymerizable compounds (B) and (B ') form a network structure in the coating film within a short time by ultraviolet irradiation while maintaining the alignment state of the block copolymer formed during heating and drying. It has the function of improving the strength of the coating film and at the same time exhibiting good antifogging properties. In order to sufficiently exhibit such a function, it is necessary that the compound is a compound represented by the above (B) or (B ′) among the photopolymerizable polyfunctional compounds.

The photopolymerizable compound (B) is composed of the compound represented by Chemical formula 4, and n is in the range of 1-30. n is 3
If it exceeds 0, the coating film strength tends to decrease. Further, the photopolymerizable compound (B ') is composed of the chemical formula 5 and exhibits excellent abrasion resistance by increasing the crosslink density of the coating film. Moreover, the surfactant as the component (E), which will be described later, is gradually transferred from the inside of the network structure to the surface of the coating film due to the interaction with the hydrophilic polymer portion of the block copolymer, and The performance that the antifogging property lasts is expressed.

When the photopolymerizable compounds (B) and (B ') are mixed and used, the higher the content of the photopolymerizable compound (B') in the coating film, the more excellent the abrasion resistance. The performance is exhibited and the higher the content of the photopolymerizable compound (B), the better the antifogging property. Therefore, the mixing ratio of the photopolymerizable compounds (B) and (B ') is appropriately determined in consideration of such points.

Next, the polar solvent which is the component (C) in the present invention will be explained. When the polar solvent (C) is released from the coating film in the heating and drying step, the hydrophobic polymer portion (b) of the block copolymer (A) or (A ′) is placed on the substrate side, and the hydrophilic solvent (C) is added. It has the function of orienting the united portion (a) or (a ') at a high concentration on the coating film surface side. In order to sufficiently exhibit this function, the polar solvent (C) depends on the composition of the block copolymer, and the hydrophilic polymer portion (a) or (a ′) is more than the hydrophobic polymer portion (b). It is necessary to select a solvent that is a better solvent.

Examples of the polar solvent (C) are alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol and diacetone alcohol, methyl cellosolve, ethyl cellosolve,
Alcohol ether solvents such as butyl cellosolve, methyl carbitol, ethyl carbitol, and butyl carbitol, amide solvents such as formamide and dimethylformamide, and nitrile solvents such as acetonitrile and acetylnitrile are used. Of these, alcohol ether solvents such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve are good solvents for the hydrophilic polymer portion rather than the hydrophobic polymer portion, and in terms of the balance of solubility for both polymer portions. Particularly preferred.

Next, the photopolymerization initiator which is the component (D) of the present invention will be described. This photopolymerization initiator (D) is
The photopolymerizable compound has a function as a polymerization initiator when it is cured by ultraviolet rays, and a conventionally known one is used.

The photopolymerization initiator (D) is, for example,
Benzoin or benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, aromatic ketones such as benzophenone and benzoylbenzoic acid, α-dicarbonyls such as benzyl, benzyl dimethyl ketal, benzyl diethyl ketal Such as benzyl ketals, acetophenone, 1- (4-dodecylphenyl)-
2-hydroxy-2-methylpropan-1-one, 1-
Hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propane-1-
On, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, 2-methyl-
Acetophenones such as 1- [4- (methylthio) phenyl] -2-morpholinopropane-1, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone and 2-t-butylanthraquinone, 2,4-dimethylthioxanthone, 2-isopropylthioxanthone,
Thioxanthones such as 2,4-diisopropylthioxanthone, 1-phenyl-1,2-propanedione-2-
Α-acyl oximes such as (o-ethoxycarbonyl) oxime, amines such as ethyl p-dimethylaminobenzoate and isoamyl p-dimethylaminobenzoate are used.

Of these, less susceptible to oxygen,
From the viewpoint of excellent curability, acetophenones such as 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, aromatic ketones such as benzophenone, and benzyl ketals such as benzyl dimethyl ketal are Particularly preferred.

Next, the surfactant which is the component (E) of the present invention will be described. This surfactant gradually interacts with the hydrophilic polymer portion of the block copolymer and gradually migrates from the inside of the coating film to the surface of the coating film, and in the block copolymer (A) or (A ′). Hydrophilic polymer part (a)
Alternatively, it exhibits the function of exhibiting antifogging property for a long period of time for two reasons that a synergistic effect with the hydrophilic property of (a ′) appears. Further, the surfactant improves the leveling property of the coating film surface, and the appearance of the coating film becomes good.

As this surfactant, a generally used non-fluorine-based surfactant, that is, an ordinary non-ionic surfactant, anionic surfactant, cationic surfactant, zwitterionic surfactant is used. In addition to the agent, a surfactant containing fluorine is selected and used. Of these,
As the fluorine-containing surfactant, a fluorine-containing surfactant in which the hydrocarbon group (alkyl group) of the generally used non-fluorine-based surfactant is substituted with a perfluoroalkyl group is preferably used.

Since this fluorine-containing surfactant has a very high surface activity, it has the property of being concentrated to a high concentration in the vicinity of the surface of the coating film when the coating film is formed by ultraviolet curing, and is thus suitable. is there. Therefore, even when a very high density mesh is formed by the component (B '), good antifogging performance can be exhibited, and compatibility between hardness and antifogging property can be achieved even better. Moreover, excellent antifogging properties can be exhibited even in a low temperature environment where it becomes extremely difficult to exhibit antifogging properties. in addition,
This fluorine-containing surfactant further improves the leveling property of the coating film surface in the presence of an appropriate amount, and further improves the coating film appearance. The behavior of the fluorinated surfactant once concentrated in the vicinity of the surface during the formation of the coating film is assumed to be the same as that in the case of the above-mentioned general surfactant when it migrates to the surface of the coating film.

Among the non-fluorine-based surfactants, examples of the nonionic surfactant include polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether,
Polyoxyethylene higher alcohol ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol, polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenol, polyoxyethylene acyl esters such as polyoxyethylene glycol monostearate, Polypropylene glycol ethylene oxide adduct, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, and other polyoxyethylene sorbitan fatty acid esters, alkyl phosphate esters,
Phosphoric acid esters such as polyoxyethylene alkyl ether phosphoric acid ester, sugar esters, cellulose ethers and the like 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, octadecylamine acetate, triethanolamine monoformate, stearamidoethyldiethylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, Dilauryl 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 dimethylalkyllaurylbetaine and dimethylalkylstearylbetaine, sulfonic acid type amphoteric surfactants such as dimethylalkylsulfobetaine, and alkylglycine. used.

As the fluorine-containing surfactant, nonionic
System, anion system, cation system, zwitterion system
One can also be used. As non-ionic type
Is C_PF_{2P + 1}C₂H_FourO (C₂H_FourO)_qH (p is 6 ~
12 is an integer, q is an integer of 3 to 30), C_PF_{2P + 1}SO₂N
(C_rH_{2r + 1}) (C₂H_FourO)_qH (p is a 6-12 integer
Number, q is an integer of 3 to 30, r is an integer of 1 to 4), C_PF
_{2P + 1}SO₃H (p is an integer of 6 to 12), C_PF_{2P + 1}CO₂H
(P is an integer of 6 to 12), C_PF_{2P + 1}SO₂N (C_rH _{2r + 1})
C₂H_FourOSO₃H (p is an integer of 6 to 12, r is 1 to 4
Integer), C_PF_{2P + 1}O-C₆H_Four-CO₂(C₂H_FourO)_qR
_S(P is an integer of 6 to 12, q is an integer of 3 to 30, R_SIs
Alkyl group having 1 to 16 carbon atoms, phenyl group or carbon number
Alkylphenyl substituted with an alkyl group of 1 to 16
Group), C_PF_{2P + 1}O-C₆H₃-[CO₂(C ₂H_FourO)_qR
 _S]₂(P is an integer of 6 to 12, q is an integer of 3 to 30, R
 _SIs an alkyl group having 1 to 16 carbon atoms, a phenyl group or
Alkyl group substituted with an alkyl group having 1 to 16 carbon atoms
Phenyl group), C_PF_{2P + 1}C₂H_FourOCONHC₆H_Four(CH₃) N
HOCO (C₂H_FourO)_qH (p is an integer of 6 to 12, q is 3 to
An integer of 30) and the like.

[0045] Of these, in addition to the solubility, in terms of coating appearance by transparency and the like of the coating _{film, C P F 2P + 1 C} 2 H 4 O (C
₂ H ₄ O) _q H (p is an integer of 6 to 10, q is 10 to 30)
_{Integer), C P F 2P + 1} SO 2 N (C r H 2r + 1) (C 2 H 4 O)
_q H (p is an integer of 6 to 10, q is an integer of 10 to 30, r
Is an integer of 1 to 3) is particularly preferable.

Examples of anionic compounds include C _P F _{2P + 1} SO
₃ M (p is an integer of 6 to 12, M is Li, Na, K, NH ₄ , NH ₃ C
₂ H ₄ OH), C _P F _{2P + 1} CO ₂ M (p is an integer of 6 to 12,
M is _{Li, Na, K, NH 4} , NH 3 C 2 H 4 OH), C P F 2P + 1 C 2
H ₄ O (C ₂ H ₄ O) _q SO ₃ M (p is an integer of 6 to 12, q
Is an integer of 3 to 30, M is Li, Na, K, NH ₄ , NH ₃ C ₂ H ₄ OH)
And the like, and any of them is preferably used.

Cation type compounds include C _P F _{2P + 1} C
₂ H ₄ SC ₂ H ₄ CO ₂ C ₂ H ₄ N (C _r H _{2r + 1} ) ₃ X (p is an integer of 6 to 12, r is an integer of 1 to 4, X is I, Br, C
l), C _P F _{2P + 1} CONHC _t H _2t N (C _r H _{2r + 1} ) ₃ X (p
6 to 12 integer, r is an integer of 1 to 4, t is an integer of from 1 to 5, X is I, Br, Cl), C P F 2P + 1 SO 2 NHC t H 2t N (
_{C r H 2r + 1) 3} X (p is integer from 6-12, r is an integer of 1 to 4, t is an integer of from 1 to 5, X is I, Br, Cl) and the like.

Examples of zwitterionic compounds include C_PF_{2P + 1}
CONHC_tH_2t N (C_rH_{2r + 1})₂C ₂H_FourCO₂(P is 6
~ An integer of 12, r is an integer of 1 to 4, and t is an integer of 1 to 5)
 , C_PF_{2P + 1}SO₂NHC_tH_2t N (C_rH_{2r + 1})₂C₂H
_FourCO₂(P is an integer of 6 to 12, r is an integer of 1 to 4, and t is
(Integer of 1 to 5) and the like.

Among the above-mentioned surfactants, from the viewpoint of appearance such as antifogging property, antifogging sustainability and leveling property of coating film, the nonionic surfactant or anion in the non-fluorine type surfactant is used. A combination of a surface-active agent and a fluorine-containing surface-active agent is preferable.

As the above-mentioned components (B), (C), (D) and (E), commercially available products can be used, or those synthesized according to a known method can also be used.
Next, the blending ratio of the components (A) to (E) will be described.

The weight ratio of the (A) / (B) or (B ') / (E) component in the first invention and the (A') / (B) or (B ') / (E in the second invention. The component weight ratio is in the range of 100/10 to 100 / 0.5 to 60. When the ratio of the component (B) or (B ') is less than 10, the cross-linking density of the coating film is low and sufficient coating film strength cannot be obtained.
If it exceeds 00, the adhesion of the coating film to the base material is deteriorated.
Further, if the ratio of the component (E) is less than 0.5, the antifogging property is insufficient, and if it exceeds 60, the coating film strength is insufficient.

The mixing ratio of the photopolymerization initiator (D) component is 1 to the total amount of the block copolymer (A) or (A ') component and the photopolymerizable compound (B) or (B'). A range of 20% by weight is preferred. If the content of component (D) is less than 1% by weight, the curing by ultraviolet rays does not proceed sufficiently and
If it exceeds the range, problems may occur in the weather resistance of the coating film.

The content of the polar solvent (C) component is preferably 30% by weight or more based on the total amount of the composition. 30% by weight
When the amount is less than 1, the orientation of the hydrophilic polymer portion and the hydrophobic polymer portion in the block copolymer (A) or (A ′) component tends to be insufficient, and the pot life and coating suitability of the coating composition are also unsatisfactory. It is easy to become enough. The upper limit is about 90% by weight in order to secure the solid content after coating.

In the ultraviolet-curable antifogging composition of the present invention, the vinyl type monomer disclosed as a monomer for forming the block copolymer (A) or (A ') component, if necessary. Can be included. However, if the vinyl-type monomer is excessively contained, the cross-linking density is lowered and the coating film strength is insufficient, or it may be necessary to lengthen the ultraviolet irradiation time. Must be set. Further, if necessary, a known photopolymerization accelerator such as a benzoic acid-based compound or a tertiary amine may be contained.

Therefore, the ultraviolet-curable antifogging agent composition of the present invention comprises the block copolymer which is the component (A) or (A ') when the polar solvent which is the component (C) is released from the coating film. The hydrophobic polymer portion (b) of (1) is oriented toward the substrate side, and the hydrophilic polymer portion (a) or (a ') is oriented toward the coating film surface side at a high concentration. Therefore, the hydrophobic polymer portion exhibits good coating strength and adhesion to the substrate, and the hydrophilic polymer portion exhibits good antifogging property.

Further, since the block copolymer itself has the chemical formula 3 exhibiting radical polymerizability, it is cross-linked inside the coating film together with the photopolymerizable compound represented by (B) or (B ') during ultraviolet curing. It hardens to form a strong network structure. Therefore, a UV-curable coating composition containing a conventional hydrophilic / hydrophobic block copolymer and a crosslinking agent (Japanese Patent Application No. 3-87).
42), the coating film strength and appearance at the time of moisture absorption are better retained.

Further, in the first invention, since the hydrophilic polymer portion (a) of the block copolymer (A) component does not participate in the crosslinking reaction and can move relatively freely in the coating film, The orientation on the surface of the coating film at the time of UV curing and the effect of imparting hydrophilicity thereto are further excellent. On the other hand, in the second invention, since the hydrophilic polymer portion (a ') of the block copolymer (A') component is partially substituted by the chemical formula 3 having a radically polymerizable unsaturated group, ultraviolet rays are The coating strength is improved when the curable coating composition is applied to a substrate and cured by UV irradiation.

On the basis of the above properties, the ultraviolet-curable coating composition of the present invention has anti-fogging properties on ski goggles, underwater glasses, helmet shields, instrument covers, lenses, windows of houses or cars, etc. Is useful for giving.

[0059]

EXAMPLES The present invention will be specifically described below with reference to Reference Examples, Examples and Comparative Examples. The number of copies is based on weight. (Reference Examples ap) (Synthesis of hydrophilic / hydrophobic block copolymer) A block copolymer was synthesized as follows by two-step polymerization using a polymeric peroxide as a polymerization initiator. The polymerization conditions shown below are conditions under which the charged monomers are almost completely polymerized at each stage.

A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 100 parts of methyl cellosolve, heated to 70 ° C. while blowing nitrogen gas, and methyl cellosolve A part [CO (CH ₂ ) _{4 (CO) O (C 2 H} 4 O) 3 - B section _{-CO (CH 2) 4 (CO} ) OO ] ₁₀ hydrophilic monomer C of hydrophobic monomer D portion AA or MAA E unit GA or GMA The mixed solution consisting of E'part was charged over 2 hours, and the polymerization reaction was further carried out for 2 hours (first stage polymerization).

Thereafter, a mixed solution of methyl cellosolve F part hydrophilic monomer G part hydrophobic monomer H part AA or MAA I part GA or GMA I'part was charged over 30 minutes and the mixture was heated at 75 ° C. for 5 minutes. A polymerization reaction was carried out for a time (second-stage polymerization). Tables 1 to 4 show the number of parts A to I'and the results of the polymerization reaction. (Reference Example q, r) (Synthesis of random copolymer) Methyl cellosolve 10 was added to the reactor used in the synthesis of Reference Example a.
0 parts were charged and heated to 85 ° C. while blowing nitrogen gas, and then methyl cellosolve 44 parts t-butylperoxyoctanoate 4 parts hydrophilic monomer C part hydrophobic monomer D part AA or MAA E part GA Alternatively, a mixed solution consisting of GMA E'part was charged over 2 hours, and the polymerization reaction was further performed for 9 hours. Table 5 shows the number of parts of C to E'and the polymerization results.

The abbreviations in Tables 1 to 5 have the following meanings. DMA: N, N-dimethylacrylamide ACMO: N-acryloylmorpholine IPA: N-isopropylacrylamide HEMA: 2-hydroxyethyl methacrylate HEA: 2-hydroxyethyl acrylate MMA: methyl methacrylate IBMA: isobutyl methacrylate AA: acrylic acid MAA: Methacrylic Acid GMA: Glycidyl Methacrylate GA: Glycidyl Acrylate Further, the solid content in the column of polymerization result represents% by weight. The viscosity represents the viscosity (P) of the polymer solution at 25 ° C. The ratio (%) of the hydrophilic polymer represents the ratio of the polymer synthesized by the first stage polymerization to the total amount of the polymer.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

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[Table 5]

Reference Examples 1 to 21, introduction of general formula 3 In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 100 parts of the polymerization solution of Reference Examples a to i or k to r AA or MAA. E part GA or GMA E'part Methyl cellosolve F part Triethylbenzylammonium chloride 3 parts p-Methoxyphenol 0.1 part Charged, heated to 90 ° C. and stirred for 10 hours, and hydrophilic / hydrophobic block copolymer or random copolymer Generalization to coalesce 3
Was introduced. The above E, E'or F used in the reaction
And the reaction results are shown in Tables 6-10.

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[Table 6]

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[Table 7]

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[Table 8]

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[Table 9]

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[Table 10]

(Examples 1 to 17 and Comparative Examples 1 to 13) The compounds shown in Tables 11 to 14 were added to the polymer solutions synthesized in Reference Example j and Reference Examples 1 to 21. Then, the hydrophilic polymer portion of the block copolymer is diluted with methylcellosolve, which is a better solvent, so that the concentration of components other than the solvent is 25% by weight, and the ultraviolet curable type is used. An antifogging composition was prepared. Next, each composition was applied to various base materials using a bar coater so that the dry film thickness was 5 μm. Then, first, heating and drying were performed at 80 ° C., and thereafter, a cured coating film was prepared by irradiating ultraviolet rays from a distance of 25 cm using a high pressure mercury lamp of 80 W / cm (manufactured by Nippon Battery Co., Ltd.). Tables 11 to 14 also show the type of the substrate, the heating and drying time, and the ultraviolet irradiation time.

The numbers of parts of the polymers in Tables 11 to 14 are the numbers converted into solids. The abbreviations have the following meanings. (Crosslinking agent) means a photopolymerizable compound and represents the following compound. : Polyethylene glycol diacrylate, trade name NK Ester A200 manufactured by Shin Nakamura Chemical Co., Ltd .: Polyethylene glycol diacrylate, trade name NK ester A600 manufactured by Shin Nakamura Chemical Co., Ltd .: Polypropylene glycol diacrylate, Shin Nakamura Chemical Co., Ltd. Product name NK ester APG400: polyethylene glycol dimethacrylate, product name NK ester 23G manufactured by Shin Nakamura Chemical Co., Ltd .: pentaerythritol triacrylate, product name NK ester A-TMM3 manufactured by Shin Nakamura Chemical Co., Ltd .: pentaerythritol. Tetraacrylate, trade name NK Ester A-TMMT (non-fluorine-based surfactant) manufactured by Shin-Nakamura Chemical Co., Ltd. (a): polyoxyethylene nonyl phenyl ether, manufactured by NOF CORPORATION Nonion HS-212 (b): Octyldecylamine acetate: Nippon Oil & Fats Co., Ltd. trade name Cation SA (c): Sodium dioctyl sulfosuccinate, Nippon Oil & Fats Co. trade name Lapizole B-80 (d): Dimethylalkyl ( Palm) Betaine, manufactured by NOF CORPORATION Anon BF (fluorine-based surfactant) (e): Perfluoroalkyl ethylene oxide adduct (EO addition mole number: about 10), manufactured by Dainippon Ink and Chemicals, Inc. Fuck F-142D (f): Potassium perfluoroalkylcarboxylate, trade name manufactured by Sumitomo 3M Fluorad FC-129 (g): Ammonium perfluoroalkylsulfonate,
Sumitomo 3M Co., Ltd. trade name Florard FC-93 (photoinitiator) (1): 2-hydroxy-2-methyl-1-phenylpropan-1-one, Merck Japan Co. trade name Darocur 1173 (2 ): 1-hydroxycyclohexyl phenyl ketone,
Product name Irgacure 18 manufactured by Nippon Ciba Geigy Co., Ltd.
4 (Substrate) PMMA: Polymethylmethacrylate, PVC: Polyvinyl chloride, PC: Polycarbonate (drying time) Heat drying time (seconds). (Irradiation time) Indicates the ultraviolet irradiation time (seconds).

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[Table 11]

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[Table 12]

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[Table 13]

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[Table 14]

The physical properties of each coating film obtained as described above were evaluated by the following evaluation methods.
The results are shown in Tables 15-17. (1) Adhesion The coating film is cut in the vertical and horizontal directions with a cutter knife to make 100 crosscuts (cut pieces) that reach the base material, and cellophane adhesive tape (manufactured by Nichiban Co., Ltd.) is attached to the adhesive surface. The number of crosscuts that were peeled in the vertical direction and remained without peeling was represented by the following symbols. (a): 100/100, (b): 80/100 or more, (c)
: Less than 80/100 (2) Coating Strength Pencil Scratch Test (Coating Hardness) A pencil scratch test according to JIS K5400 was performed and judged according to the following criteria.

Water resistance The appearance of the coating film after being immersed in warm water at 60 ° C. for 100 hours was visually observed and judged according to the following criteria.

◯: No change in appearance, ×: Change in appearance (3) Effect of moisture absorption Coating strength The coating was left for 1 week in an environment of a temperature of 40 ° C. and a relative humidity of 95%. Immediately after that, a pencil scratching test according to JIS K5400 was performed, and judgment was made according to the above criteria.

Appearance change (haze value) The appearance change of the coating film after being left in an environment of a temperature of 40 ° C. and a relative humidity of 95% for 1 week was measured by a direct-reading haze meter (manufactured by Toyo Seiki Seisakusho Co., Ltd.). did. It should be noted that this value is generally 1.0 or less, and if it exceeds 1.0, it is determined that the appearance is poor. (4) Antifogging Property Normal Temperature Breathing Test A film was blown in a thermostatic chamber at 20 ° C. and a relative humidity of 50%, and the state of haze was visually evaluated according to the following criteria.

⊚: No fog at all, ◯: Water droplets wet and spread instantly, Δ: Some fog is seen, ×: All over cloudy low temperature exhalation test 0 ° C, relative humidity 80% The membrane was blown and the cloudiness was visually evaluated according to the above criteria.

Antifogging Sustainability The coating film was immersed in water at 30 ° C. for 24 hours and then naturally dried,
The above breath test was performed.

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[Table 15]

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[Table 16]

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[Table 17]

As shown in Tables 15 to 17 above, the cured coating films formed by coating the ultraviolet curable antifogging agent compositions of Examples 1 to 17 showed excellent adhesion, hardness and water resistance. It can be seen that the film has excellent coating strength and good anti-fogging property. In addition, it should be noted that there is little decrease in coating film hardness and change in appearance when absorbing moisture. Further, this cured coating film can be obtained by irradiation with ultraviolet rays at a very short processing speed, as compared with a conventional heat-curable antifogging composition which requires a processing speed of 30 minutes or more for curing.

In addition, the compositions of Examples 1, 2 and 5-9, which are the first invention, were generally protected from the compositions of Examples 3, 4 and 10-17, which were the second invention. Excellent effect of imparting cloudiness. The reason is that in the compositions of Examples 1, 2 and 5 to 9 which are the first invention, the hydrophilic polymer portion does not participate in the cross-linking reaction and relatively freely moves within the coating film, so that the coating is performed. This is probably because the orientation to the film surface is high. on the other hand,
In the compositions of Examples 3, 4 and 10 to 17 which are the second invention, the coating film strength is generally higher than that of the compositions of Examples 1, 2 and 5 to 9. The reason is that Examples 3, 4, and 10
It is considered that in the compositions of Nos. 17 to 17, both the hydrophilic polymer portion and the hydrophobic polymer portion participate in the crosslinking reaction.

In addition, the compositions of Examples 5 to 17 exhibited antifogging properties as compared with the compositions of Examples 1 to 4 due to the action of the fluorine-containing surfactant having a very high surface activity. Excellent anti-fogging property can be exhibited even in a low temperature environment where it becomes extremely difficult.

In contrast to these results, the ultraviolet-curable antifogging agent composition falling outside the scope of the present invention causes various problems in performance as shown in Table 17. That is, when a block copolymer not containing the general structural formula 3 showing radical polymerizability is used (Comparative Example 1), the coating strength is significantly reduced and the appearance is significantly changed when moisture is absorbed. Also, when the amount of introduction of the chemical formula 3 is less than the range of the present invention (Comparative Example 2), the decrease in the coating film hardness and the change in the appearance during moisture absorption are remarkable. On the contrary, when the introduction amount of Chemical formula 3 is larger than the range of the present invention (Comparative Example 3,
4) Adhesion and antifogging property are reduced.

The ratio of the hydrophilic monomer selected from N-substituted or unsubstituted (meth) acrylamide compounds and hydroxyalkyl (meth) acrylate in the hydrophilic polymer portion (a) or (a ') is 50% by weight. When it is less than 0.1% (Comparative Example 5), the antifogging property is lowered. When the ratio of the hydrophilic polymer portion in the block copolymer is higher than the range of the present invention (Comparative Example 6), the adhesion and the water resistance are deteriorated.

On the contrary, when the ratio of the hydrophilic polymer is less than the range of the present invention (Comparative Example 7), the antifogging property is insufficient. When a random copolymer is used (Comparative Examples 8 and 9), the effect of imparting antifogging property is low and the performance is generally insufficient.

When the amount of the photopolymerizable compound (B) or (B ') used is less than the range of the present invention, that is, when it is not used (Comparative Example 10), the coating film hardness becomes insufficient,
On the contrary, when the amount is more than the range of the present invention (Comparative Example 11), the adhesion and the antifogging property are insufficient.

When the surfactant (E) component is less than the range of the present invention, that is, when it is not used (Comparative Example 1)
2) The antifogging property becomes insufficient. On the contrary, when it is more than the range of the present invention (Comparative Example 13), the coating film hardness and water resistance are insufficient (Comparative Example 13).

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As described in detail above, the ultraviolet-curable antifogging agent composition of the first invention can impart good antifogging property to the surface of various materials, exhibit adhesion and coating strength, and Particularly, even in a high-humidity environment, good transparency can be maintained, appearance quality can be ensured, and a decrease in coating film strength can be effectively prevented.

The UV-curable antifogging agent composition of the second invention can exhibit antifogging property, adhesiveness and coating film strength, and can secure good appearance quality even in a high humidity environment, and in particular, a coating film. It has an excellent effect of improving strength.

Therefore, the ultraviolet-curable antifogging agent composition of the present invention imparts antifogging property to a substrate such as ski goggles, underwater glasses, helmet shield, instrument cover, lens, house or car window. Useful for.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI technical display location // C08F 299/00 MRN 7442-4J 299/02 MRS 7442-4J (72) Inventor Hiroshi Omura Aichi 5-3 Rokukanyama, Taketoyo-cho, Chita-gun, Japan

Claims (2)

[Claims] 1. A block copolymer represented by the following component (A), a photopolymerizable compound represented by the following component (B) or (B ′), and a hydrophobic property in the block copolymer (A). The polar solvent (C), which is a good solvent for the hydrophilic polymer portion rather than the polymer portion, the photopolymerization initiator (D), and the surfactant (E), and the solid content weight ratio. Is (A) component / (B) or (B ′) component / (E) component =
The ultraviolet-curable antifogging agent composition, which is 100/10 to 100 / 0.5 to 60. Component (A) One or more kinds of hydrophilic monomers selected from N-substituted or unsubstituted (meth) acrylamide compounds represented by the following general formula 1 or 2 and hydroxyalkyl (meth) acrylate 50 wt. % Or more of the hydrophilic polymer portion (a), and a hydrophobic polymer portion (a) formed of a hydrophobic monomer and containing 5 to 50% by weight of a portion having the following general formula 3 as a structural unit ( b) and a hydrophilic polymer part (a)
And the weight ratio of the hydrophobic polymer portion (b) is 90/10 to 3
A block copolymer of 0/70. [Chemical 1] In the above formula, R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom, a linear or branched C _n H _{2n + 1} , R ₃ is a hydrogen atom, a linear or branched C _n H _{2n +1,} N, N-dimethylaminopropyl group or _{-C (CH 3) 2 CH 2} COCH
Represents ₃ . However, n is an integer of 1 to 4. [Chemical 2] In the above formula, R ₁ is a hydrogen atom or a methyl group, and X is-.
_{(CH 2) 4 -, -} (CH 2) 5 - or - (CH _{2) 2}
-O- (CH _{2) 2} - represents a. [Chemical 3] In the above formula, R ₁ and R ₄ represent a hydrogen atom or a methyl group. Component (B) A photopolymerizable compound represented by the following general formula 4 In the above formula, R ₁ and R ₄ are a hydrogen atom or a methyl group, n
Is an integer of 1 to 30. Component (B ') Photopolymerizable compound represented by the following general formula 5 In the above formula, R ₁ is a hydrogen atom or a methyl group, m is 0,
Represents 1 or 2. 2. The ultraviolet-curable antifogging agent composition according to claim 1, wherein the block copolymer (A) is a block copolymer represented by the following (A ′). Component (A ′) One or more hydrophilic monomers selected from N-substituted or unsubstituted (meth) acrylamide compounds represented by the general formula 1 or 2 and hydroxyalkyl (meth) acrylate 50 A hydrophilic polymer portion (a ') containing 5 to 50% by weight of a portion having the structural unit represented by the general formula 3 as a structural unit, and a hydrophobic monomer. A hydrophobic polymer portion (b) containing 5 to 50% by weight of a portion having the chemical formula 3 as a structural unit, and the weight ratio of the hydrophilic polymer portion (a ') to the hydrophobic polymer portion (b) is 90. /
A block copolymer of 10 to 30/70.