JPH01165674A - Anti-fogging coating material for inorganic glass - Google Patents

Abstract

PURPOSE:To obtain the title coating material which can give a coating film having excellent marring resistance and persistence of antifogging properties, and good transparency, boiling water resistance, adhesiveness, etc., by using a specified undercoating agent and a specified top coating agent as its constituents. CONSTITUTION:The title coating material consists of an undercoating agent containing a copolymer (A) of a (meth)acrylic ester and a hydroxylated polymerizable unsaturated compound, a silane coupling agent (B) of formula I, a dicyclopentenyloxy(alkyl) (meth)acrylate monomer (C) of formula II and, if required, a curing catalyst (D); and a top coating agent containing a polyfunctional (meth)acrylate monomer (E) of formula III, a phosphate monomer (F) of formula IV and, if required, a curing catalyst (G) and a trifunctional monomer (H) comprising a glycerin glycidyl ether acrylate of formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an antifogging coating agent for inorganic glass that has excellent durability such as scratch resistance and boiling water resistance.

(Conventional technology and problems) Transparent inorganic glass materials are used in various fields.

However, these transparent inorganic glass materials have the disadvantage that they become cloudy due to dew condensation when the surface temperature falls below the dew point of the environment.

Methods to prevent such fogging include placing a hot wire inside the glass to keep the temperature of the glass surface above the dew point, and applying an anti-fog agent to the glass surface, but the former method is extremely expensive. The latter has the disadvantage that it is difficult to obtain a surface that is excellent in both surface scratch resistance and antifogging durability.

For this reason, the applicant has already filed an application for a composition that improves these drawbacks (Japanese Patent Application No. 94638/1982).

That is, this improved antifogging composition is made by adding a specific silane coupling agent to a copolymer consisting of a (meth)acrylic acid ester and a hydroxyl group-containing synthetic unsaturated compound, and further adding a curing catalyst if necessary. The added primer, a specific phosphoric acid ester monomer is added to the specific polyfunctional (meth)acrylate monomer, and if necessary, a curing catalyst and a specific trifunctional acrylic acid ester monomer are added. It has excellent scratch resistance and anti-fog durability.
Moreover, it has the advantage of being excellent in transparency, adhesion, and moisture resistance, as well as good coating film properties such as heat cycle resistance, and excellent durability.

However, even though this composition has excellent durability, it is insufficient in adhesion and durability of coating film hardness in applications requiring severe conditions such as immersion in boiling water.

(Means for solving the problem) In view of this situation, the present inventors have conducted intensive research and have identified a copolymer consisting of a (meth)acrylic acid ester and a hydroxyl group-containing polymerizable unsaturated compound. silane coupling agents and certain dicyclopentenyloxy(alkyl)(
A primer containing meth)acrylate and, if necessary, a curing catalyst, a specific polyfunctional (meth)acrylate monomer, a specific surface-active group-containing phosphate monomer, and further When using a top coat containing a curing catalyst and a specific trifunctional acrylic acid ester monomer, it has excellent scratch resistance and anti-fog durability, as well as transparency, adhesion, and moisture resistance. The present inventors have discovered that it is possible to obtain an antifogging coating agent for inorganic glass that has excellent coating properties such as boiling water resistance and heat cycle resistance, and is excellent in durability, leading to the completion of the present invention.

That is, the present invention provides (A) a copolymer consisting of a (meth)acrylic acid ester and a hydroxyl group-containing polymerizable unsaturated compound, (B) - maximum (
1) %Formula%(1) (However, Y in the formula is a vinyl group, acrylic group, mercapto group, amino group, R1 is -CH2-1-CH2-CH2
-1-CH2-CH2-CH2-, X is -QC)
I3- or -0CH2CH.

may be the same or different. ), and (C) - maximum (If) (wherein R2 represents a hydrogen atom or a methyl group,
R5 is 10-1-CH20-1-CH2CH20-1C
H5CH2 ■ CH.

Socyclopontenyloxy(alkyl) represented by (
meth)acrylate monomer, further containing (D) a curing catalyst as necessary, and (G) / (B) / (C'l
is in a weight ratio of 40/10150 to 94/115, and / // (T)- (Odor - maximum (m) The remainder is a hydroxyl group, and n is an integer of 1 to 5.] A polyfunctional (meth)acrylate monomer represented by (F) - maximum (■) (However, R4 in the formula is a hydrogen atom or a methyl group shows,
Each of R may be the same or different, and each of R may be the same or different. Moreover, m represents an integer of 1 to 50. ) A phosphate ester monomer represented by (4), optionally (G) a curing catalyst and (6)-maximum (V) H H (where t in the formula represents an integer of 1 to 5). ], and (g) / (F) / (6) has a weight ratio of 90/1010 to 10/30/60. The present invention provides an anti-fog coating agent for inorganic glass characterized by comprising a top coating agent.

Incidentally, if necessary, a solvent and known additives such as a leveling agent, an ultraviolet absorber, an antioxidant, a surfactant, and the like may be added to this coating agent.

Copolymers used in the undercoat in the present invention (specific examples of N include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and globil (meth)acrylate; copolymers consisting of hydroxyl group-containing polymerizable unsaturated compounds, particularly preferred are copolymers consisting of methyl methacrylate and β-hydroxyethyl (meth)acrylate and/or β-hydroxyglobil (methacrylate). .

Specific examples of the hydroxyl group-containing polymerizable unsaturated compound used in the production of the copolymer (4) include β-hydroxyethyl (
Metacoacrylate, β-hydroxyglobil (meth)
Acrylate; 1,6-hexanediol mono(meth)acrylate obtained by partial esterification of polyhydric alcohol and (meth)acrylic acid, neopentyl glycol mono(meth)acrylate, 1,4-butanediol mono( meth)acrylate, trimethylolpropane(
Meth)acrylate, intererythritol (meth)acrylate; further examples include compounds obtained by addition reaction of butylglycidyl ether, persatic acid glycidyl ester, or phenylglycidyl ether with (meth)acrylic acid.

Specific examples of the silane coupling agent (B) represented by general formula (1) used in the undercoat in the present invention include vinyltrichlorosilane/, vinyltriethoxysilane, vinyltrimethoxysilane, and vinyl-tris(β-methoxysilane). ethoxy)silane, γ-methacryloxyglobiltrimethoxysilane, γ-mercaptoglobiltrimethoxysilane, γ-aminoglopyltriethoxysilane, N-β-
(aminoethyl)-r-aminoglopyltrimethoxysilane and the like, among which γ-mercagutoglobiltrimethoxysilane is preferred.

As the dicyclopentenyloxy(alkyl)(meth)acrylate monomer (C) of the general formula (n) used in the undercoat in the present invention, any one represented by -maximum (■) is preferable. Among them, R in maximum (n) is a hydrogen atom and R3 is -CH2CH20
- Compounds are particularly preferred.

Specific examples of the polyfunctional (meth)acrylate monomer (6) represented by the general formula ([I) used in the topcoating agent in the present invention include trimethylolmeth/tetra(methacrylate), trimethylolpropanetri(meth)acrylate, trimethylolpropanetri(meth) ) acrylate, trimethylolethane tri(meth)acrylate,
Intaglycerol tri(meth)acrylate, (metaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-metaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) acrylates, among which trimethylolmethanetetra(meth)acrylate, intererythritol tetraacrylate, dipentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate are particularly preferred. Pentaerythritol hexaacrylate.

Phosphoric ester monomers (T) represented by the general formula (IV) used in the top coating agent in the present invention can preferably be used, - R4 in (IV) is a hydrogen atom or H3, and m is an integer of 10 to 25, and particularly preferred are compounds in which R4 is a methyl group and R5 is H3. The protective coating agent of the present invention consisting of the above-mentioned -
By further adding the trifunctional monomer (b) of acrylic acid ester of glycerin glycylate ether represented by maximum (V), the antifogging durability can be synergistically improved. Among these, particularly preferred are those where t in the formula is 1.

The usage ratio of (4)/(6)/(0 in the primer is (4)
), (B), and (C) totaling 11,100% by weight, usually (4) is 40 to 94% by weight and (B) is 1 to 10% by weight.
, (0 is 5 to 50% by weight, but (A) is 6% by weight)
7-82% by weight, (B) 3-8%, (Q 15-82% by weight)
25% of heavy scenes are heavy electric. In addition, the usage rate of (4) is 40i
If the amount is less than i% by weight, the antifogging property will decrease, and if it exceeds 94% by weight, the water-forming adhesion to the inorganic glass will decrease, so these are not preferred. Furthermore, if the proportion of (B) used is less than 1% by weight, the initial adhesion with the inorganic glass will decrease, and if it exceeds 10% by weight, the storage stability of the coating agent will decrease, which is not preferable. Furthermore, if the proportion of (C) used is less than 5% by weight, the water-forming adhesion with the inorganic glass will be reduced, and if it exceeds 50% by weight, the initial adhesion with the inorganic glass will be reduced, which are both undesirable.

The usage ratio of (G), (F'') and (G) in the top coat is:
The total amount of (E), (g) and (6) is 100% by weight, usually (6) is 10 to 90% by weight, and heavy electric) is 10 to 30% by weight.
(6) is 0 to 60% by weight, but when (6) is not used, (g) is preferably 70 to 80% by weight, and (takumi is preferably 30 to 20% by weight). , when using wholesale, 20 to 45% by weight of @), 13 to 25% by weight of (g), and 42 to 55% by weight of (b) are particularly preferred.

In addition, if the proportion of (E) used is less than 10% by weight, the scratch resistance will decrease, and if it exceeds 90% by weight, the antifogging property will decrease.
Each is undesirable. Also, the usage ratio of (F') is 1
If the weight is less than 0 weight, the antifogging property will decrease, and if it exceeds 30 weight, the scratch resistance and adhesion with the primer will decrease.
Each is undesirable.

Solvents used as necessary in the present invention include, for example, aromatic hydrocarbons such as toluene and xylene for the undercoat; ketones such as methyl ethyl ketone and methyl isobutyl ketone, and for the top coat. For example, alcohols such as methanol, ethanol, N-butyl alcohol, and isoglobil alcohol; aromatic carbonized water scales such as toluene and xylene; ketones such as methyl ethyl ketone and methyl ethyl isobutyl ketone; ethyl acetate and butyl acetate. , methyl cellosolve acetate,
Examples include esters such as ethyl cellosolve acetate. The solvent used for these undercoat or topcoat may be used alone or in combination of two or more kinds of gold.

Applying the antifogging coating agent of the present invention to an inorganic glass molded product,
In order to form a crosslinked cured film, ultraviolet rays, electrons,
W or radiation irradiation is required.

Among these, a curing method using ultraviolet irradiation is particularly preferred from a practical standpoint; in this case, it is necessary to add a curing catalyst that generates radicals upon irradiation with ultraviolet rays to the undercoat and topcoat.

Specific examples of this curing catalyst) or (G) include pentuphenone, p-chlorobenzophenone, 4,4'-bis(noethylamino)pe/dipheno/, benzoin, benzoin ethyl ether, acetophenone, 2-chlorothioxanthone, Examples include abstracted and cleaved carbinyl compounds such as -ethyl anthraquinone, 2-aminoanthraquinone, 2-chloroanthraquinone, and α-hydroxyisobutylphenone, and sulfur compounds such as tetramethylthiuram and nosulfide. These curing catalysts may be used alone or in combination of two or more.

The amount of these curing catalysts used is based on 100 parts by weight of the resin solid content of the undercoat consisting of (A), (B) and (C), and the amount of the topcoat consisting of (6), (F) and (6). The amount is usually 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, per 100 parts by weight of the resin solid content. If the amount used exceeds 5 parts by weight, the moisture resistance and weather resistance of the coating film may be reduced.
This is not preferred as it may discolor the paint film.

The inorganic glass molded product to which the antifogging coating agent of the present invention is used may be any product as long as it is manufactured from inorganic glass.
For example, various window glasses, instrument covers, mirrors, etc. can be used.

The anti-fog coating of the present invention can be applied to various inorganic glass molded products by, for example, applying an undercoat, curing it to at least a level that allows for the application of a topcoat, then applying the topcoat and completely curing the product. Just let it happen.

Coating methods include, for example, spray coating, dip coating, roll coater coating, flow coater coating, spin coater coating, etc., and may be selected as appropriate depending on the shape of the object to be coated.

The coating film thickness is 1 to 20 μm for the base coat and 1 to 20 μm for the top coat.
10μm is suitable, but especially adhesion, scratch resistance,
In terms of anti-fog properties and durability, the undercoat should be 10 to 15 μm thick.
The thickness of the top coat agent is preferably 3 to 7 μm.

(Example) The present invention will be specifically explained below using reference examples, examples, and comparative examples. All parts in the examples are by weight.

Reference Example 1 [Production of copolymer (4) consisting of (meth)acrylic acid ester and hydroxyl group-containing polymerizable unsaturated compound] 95 parts of methyl methacrylate and β-hydroxyethyl methacrylate were placed in a four-bottle flask equipped with a condenser and a stirrer. 5!5, 0.6 parts of n-dodefurmer butane was charged, and the reaction was carried out at 95°C for 8 hours under a nitrogen stream. When the viscosity reached 8 poise, 50 pp of hydroquinone, a polymerization inhibitor, was added.
m was added and cooled to obtain an acrylic copolymer (A-1).

Reference example 2 (same as above) Reference example 1 except that β-hydroxyglobyl acrylate was used instead of β-hydroxyethyl methacrylate
An acrylic copolymer (A-2) was obtained in the same manner as above.

Examples 1 to 5 and Comparative Examples 1 to 5 Each raw material was blended with the undercoat composition and topcoat composition shown in Table 1 to prepare antifogging coating agents for the present invention and comparison.

Next, an undercoat was applied to the inorganic glass plate using a bar coater, and after drying at 80°C for 5 minutes, it was exposed to ultraviolet light for 7 seconds using an 80W/cm high-pressure mercury lamp (manufactured by Nippon Battery Co., Ltd.). After irradiating with fs, a top coat agent was applied with a percoater, and after leaving it at 80 ° C. for 5 minutes, it was irradiated with ultraviolet rays for 10 seconds with an 80 W / α high pressure mercury lamp to obtain an inorganic glass plate with a cured coating film. Performance was evaluated by the following test. The results are shown in Table-2.

(1) Adhesion test: Make a cut from the dressing surface to the underlying synthetic resin so that there are 100 squares at the 1, 5 +・Peel off the tape vigorously,
First, count the remaining number of eyes and express it with 100 as the denominator.

(2) Paint film hardness test: According to JIS K-5400, the pencil hardness is measured under a load of 1 t.

(3) Scratch resistance test: The painted surface was strongly scratched with a nail, and the scratch resistance was evaluated with the naked eye on the following four scales.

◎...No scratches are observed.

○: Some scratches are observed.

Δ...Flaws are observed.

×: Significant scratches are observed.

(4) Anti-fog test: temperature 10℃, relative humidity 65% R1 (
After leaving the sample in a constant temperature and humidity chamber for 10 minutes, the paint surface showed a difference of 0.5 to 1.0111! Expired air was blown from a distance of H, and fogging was visually evaluated on the following four scales.

◎...FIk is not observed at all.

○...Slight calming is observed.

Δ...Yellowness is observed.

×: Significant damage is observed.

(5) Humidity test = 70℃, relative humidity 100%RH
After leaving the sample in a constant temperature and humidity chamber for 300 hours and 500 hours, adhesion, coating hardness, and antifogging properties were measured in the same manner as above.

(6) Heat cycle resistance test: Heat cycle tester (programmed constant temperature and humidity chamber GLP-44 manufactured by Irie Seisakusho)
), 70°C x 20% RH x 3 hours → 23'CX7
5%RH x 1 hour → -30℃ x 3 hours → 23℃ x 75%
RHX 1 hour → 70℃ x 95%RHX 15 hours → 23℃
After repeating 6 cycles of 1 hour of X75%IX, adhesion, coating hardness, and antifogging properties were measured in the same manner as above.

(Power boiling water adhesion test: Using a water bath, 98~
Place the sample vertically in a 100°C ring water bath and boil for 4 hours. Thereafter, after being left at room temperature for 2 hours, adhesion and coating film hardness were measured at the same 5K as above.

Hata 1) UV7000B: Goselac UV700
0B [Urethane acrylic monomer manufactured by Nippon Gosei Kagaku Co., Ltd.] *2) FA-512A: Hytaloid FA-512
A [Dicyclopentenyloxy-ethyl acrylate manufactured by Hitachi Chemical Co., Ltd.] *3) FA-511A: Hytaloid FA-511
A [Hitachi Chemical Co., Ltd. 1M dicyclopentenyloxy-acrylate] *4) DPHA: Bentadierythritol hexaarylate [manufactured by Nippon Kakei Co., Ltd.] *5) A-TMMT: ) Limethylolmethane tetraacrylate [ Shin Nakamura Chemical Co., Ltd.] 06) PTA knee ('ntaerythritol tetraacrylate [manufactured by Shin Nakamura Chemical Co., Ltd.] *7) 229E: New Frontier A-22
9E [Phosphate ester monomer manufactured by Daiichi Kogyo Seiyaku Co., Ltd. In the general formula (R/), R4 is a methyl group and R5 is -C
Compound where H-CH2-1m is 20] CH.

Hata 8) DA-314: Bunacool acrylic) D
A-314 [Trifunctional monomer of glycerin glycidyl ether acrylic acid ester manufactured by Sugase Kasei Co., Ltd., compound with t=1 in general formula (IV)] (Effects of the invention) Inorganic glass barrier of the present invention The coating film obtained from the fogging coating agent has excellent scratch resistance and anti-fogging durability, as well as transparency, adhesion to dehydration, moisture resistance, heat cycle resistance, etc. It has good physical properties and has the advantage of being extremely durable.

Claims (1)

[Claims] (A) A copolymer consisting of a (meth)acrylic acid ester and a hydroxyl group-containing polymerizable unsaturated compound, (B) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...・(I) (However, Y in the formula is a vinyl group, acrylic group, mercapto group, amino group, R^1 is -CH_2-, -CH_2-
CH_2-, -CH_2-CH_2-CH_2-, and X^1 represents -OCH_3 or -OCH_2CH3, which may be the same or different. ), and (C) general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (However, R^2 in the formula is a hydrogen atom or a methyl group. and R^3 is -O-, -CH_2O-, -CH_2CH_
2O-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. ) dicyclopentenyloxy(alkyl) (
meth)acrylate monomer, further containing (D) a curing catalyst as necessary, and (A)/(B)/(C) in a weight ratio of 40/10/50 to 94/1/5. A primer that is
(E) General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) [However, in the formula, at least three of X^2 are (meth)acryloyloxy groups and the rest are hydroxyl groups, n represents an integer from 1 to 5. ] Polyfunctional (meth)acrylate monomer represented by (F) General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(IV) (However, R^4 in the formula is hydrogen It represents an atom or a methyl group, which may be the same or different, and R^5 is -CH
＿２−CH＿２−, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, which may be the same or different. Further, m represents an integer of 1 to 50. ) Phosphate ester monomer represented by (G) curing catalyst and (H) general formula (V) ▲ Numerical formulas, chemical formulas, tables, etc.▼... (V) (However, (l in the formula represents an integer of 1 to 5), and (E)/(F)/(H) is a weight ratio An anti-fog coating agent for inorganic glass, characterized in that it consists of a topcoat agent having a coating composition of 90/10/0 to 10/30/60.