JPS63151901A - Plastic mirror - Google Patents

Abstract

PURPOSE:To improve wear resistance, anti-clouding and antistatic properties by forming a vacuum-deposited reflecting film on one side of a plastic substrate and the cured film of a cross-linkable resin material consisting of a specified compd., a specified monomer, a phosphoric ester type monomer, (meth) acrylamide and an ethanolamine compd. on the other side of the substrate. CONSTITUTION:A vacuum-deposited reflecting film is formed on one side of a plastic substrate. The cured film of a cross-linkable resin material consisting of, by weight, 30-80wt% compd. having two or more acryloyloxy and/or methacryloyloxy groups in one molecule, 20-60% monomer represented by formula I, 1-10wt% phosphoric ester type monomer represented by formula II, 1-5wt% (meth)acrylamide having a hydroxy group and 1-10wt% ethanolamine compd. is formed on the other side of the substrate. In the formulae I, II, R1 is H or methyl, R2 is alkoxy or the like and R3 is H or methyl. The wear resistance, anti-clouding and antistatic properties of the resulting plastic mirror can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a synthetic resin mirror, and more particularly to a synthetic resin mirror that has excellent abrasion resistance, antifogging properties, and antistatic properties.

[Conventional technology]

2. Description of the Related Art Conventionally, mirrors made of synthetic resin, in which a vacuum-deposited film of aluminum or the like is formed on methacrylic resin, have been widely used because they are lightweight, hard to break, and easy to process. However, since conventional mirrors of this type use methacrylic resin, scratches occur on the surface during use, and the surface resistivity is high and antistatic properties are poor, making it easy for dirt and dust to adhere. Furthermore, since the surface is hydrophobic, fine condensation may form on the surface when exposed to high temperature, high humidity environments, or conditions below the dew point.

[Problem that the invention seeks to solve]

The object of the present invention is to overcome the above-mentioned conventional techniques and provide a synthetic resin mirror that is wear-resistant, has excellent antifogging properties, and antistatic properties.

[Means for solving problems]

The synthetic resin mirror according to the present invention has a vacuum-deposited reflective film formed on one side of a synthetic resin base, and (1) two or more acryloyloxy groups in one molecule and a vacuum-deposited reflective film on the other side of the synthetic resin base. /or Compound 30 having a methacryloyloxy group
~80% by weight (2) The following general formula (wherein R8 is a hydrogen atom or a methyl group, R2 is an alkoxy group having 1 to 5 carbon atoms, an acryloyloxy group, or a methacryloyloxy group, and n is 5 to 5% by weight) (3) 20 to 60 parts by weight of a monomer represented by the following general formula (wherein R8 is a hydrogen atom or a methyl group,
(Rs is the same as R8, and m and n are integers of 1 to 15) 1 to 10% phosphoric acid ester monomer (4) Hydroxyl group-containing acrylamide or hydroxyl group-containing methacrylamide 1 5% by weight and (5) 1 to 10% by weight of an ethanolamine compound.

The synthetic resin base used for forming the synthetic resin mirror of the present invention is not particularly limited, and examples thereof include polymethyl methacrylate, a copolymer of methyl methacrylate and an acrylic ester, polystyrene, styrene and methacrylic acid. Examples include copolymers with methyl and polycarbonates.

The synthetic resin base is not particularly limited as long as it has a shape that can be used as a mirror, and may be flat or curved.

The vacuum evaporation reflective film can be formed on one side of the synthetic resin substrate by a known vacuum evaporation method using a metal such as aluminum or copper.

The cross-linked cured film formed on the other side of the synthetic resin substrate is made of a cured resin material that can be cured and impart abrasion resistance, antifogging properties, and antistatic properties to the film.

Examples of compounds having two or more 7-acryloyloxy groups and/or methacryloyloxy groups in one molecule constituting the crosslinkable resin material (hereinafter referred to as polyfunctional compounds) include ethylene glycol diacrylate and ethylene glycol dimethacrylate. , diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol diacrylate, propylene glycol diacrylate, tetrapylene glycol dimethacrylate, tripropylene glycol diacrylate , tripropylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, bentanediol diacrylate, bentanediol methacrylate, hexanediol diacrylate, hexanediol dimethacrylate, glycerin diacrylate, glycerin dimethacrylate, methoxydiethylene glycol diacrylate, Methoxydiethylene glycol dimethacrylate, 2,2-bis(4-acryloyloxyphenyl)propane, 2,2-bis(4-acryloyloxyjethoxyphenyl)propane, 2,2-bis(4-methacryloyloxyjethoxyphenyl)propane ,2,
2-bis[4-acryloyloxy(2-hydroxypropoxy)phenyl]furopane, 2-(4-acryloyloxyjetoxyphenyl)-2-(4-acryloyloxyethoxyphenyl/L/)propane, 2-(4 −
methacryloyloxypropoxyphenyl)-2-(4
-acryloyloxypropoxyphenyl)propane,
Trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diglycerin tetraacrylate, diglycerin tetramethacrylate,
Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate; = CM-COO- group or CH, =
dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, represented by C(CH,) COO- group, and the remainder are 10H groups);
dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol triacrylate,
Tripentaerythritol trimethacrylate, tripentaerythritol tetraacrylate, tripentaerythritol tetramethacrylate, tripentaerythritol pentaacrylate, tripentaerythritol pentaacrylate, tripentaerythritol hexaacrylate, tripentaerythritol hexamethacrylate; trimethylolethane, trimethylolpropane, Examples include unsaturated polyesters obtained by reacting polyhydric alcohols such as glycerin or pentaerythritol with acrylic acid or methacrylic A/acid and polycarboxylic acids such as malonic acid, succinic acid, adipic acid, glutaric acid or sebacic acid. It will be done.

The above polyfunctional compound can be used alone or in combination with other monofunctional polymerizable compounds such that at least 30% by weight of at least one of the above compounds is contained. The combined use of a monofunctional polymerizable compound in the crosslinkable resin material improves the adhesion between the synthetic resin mirror substrate and the cured film.

In particular, among the above polyfunctional compounds, from the viewpoint of abrasion resistance, adhesion to a synthetic resin mirror substrate, transparency, etc., one molecule has three or more acryloyloxy groups and/or methacryloyloxy groups. A crosslinkable resin material containing at least 30% by weight of at least one compound is preferred.

Further, from the viewpoint of workability and reduction in running costs, it is particularly preferable to use a compound represented by the general formula (1). These compounds are easily cured by irradiation with active energy rays in normal air, even if the curing atmosphere is not an inert gas atmosphere such as nitrogen or argon, forming a crosslinked cured film with excellent smoothness and uniform thickness. However, it is possible to manufacture a mirror with low resolution and no optical distortion.

Also, two or more acryloyloxy groups and/or
Or, as a monofunctional compound that can be used in combination with a polyfunctional compound having a methacryloyloxy group,
For example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, Propylene glycol acrylate, tripropylene glycol methacrylate, glycidyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 1,4-butylene glycol acrylate, 1t4-phthylene glycol methacrylate, ethyl carpitol acrylate, ethyl carpitol methacrylate, etc. It will be done. These compounds are used alone or in combination of two or more in an amount of 70 M% or less in the crosslinkable resin material.

The monomer represented by the above general formula (1) used to constitute the crosslinkable resin material has a degree of ring-opening polymerization n of ethylene oxide of 5 to 30, and a monomer of acrylic acid or methacrylic acid of polyethylene glycol. Mono or diester. If n is less than 4, the hydrophilicity will be low and the antifogging effect will not be sufficient, and if n exceeds 30, the smoothness and abrasion resistance of the cured film will also decrease. Preferred monomers represented by the general formula (1) include dimethacrylic acid or diacrylic acid of polyethylene glycol with n = 9 to 23.

The phosphoric acid ester monomer represented by the general formula ([1)] is
At least one acryloyloxy group and/or
or having a methacryloyloxy group, examples of which include acryloyloxyethyl phosphate, methacryloyloxyphosphate, acryloyloxypropyl phosphate, methacryloyloxypropyl phosphate, acryloyl oxybutyl phosphate, methacryloyloxybutyl phosphate, etc. can be given. Among phosphate compounds, those having no acryloyloxy group or methacryloyloxy group in the molecule, such as halogenated vinyl phosphates and alkyl-substituted vinyl phosphates, do not have sufficient air curing properties and antistatic properties.

In addition, the hydroxy group-containing acrylamide or hydroxyl group-containing methacrylamide (hereinafter referred to as a (meth)acrylamide compound) to be used preferably has the following general formula (wherein R6 is a hydrogen atom or a methyl group, and R1 is A hydrogen atom or a hydroxylalkyl group having 1 to 8 carbon atoms, R8+ RIG is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydroalkyl group, and Ro is a hydroxyl group or a hydroalkyl group having 1 to 8 carbon atoms. The monomer of Among these monomers, N-(hydroxymethyl)acrylamide, N-
(2-hydroxyethyl)acrylamide, N-(2-
hydroxypropyl)acrylamide, N-(1,1-
dimethyl-2-hydroxyethyl)acrylamide, N
-(1-ethyl-2-hydroxyethyl)acrylamide, N-(1,1-dimethyl-3-hydroxybutyl)acrylamide, N-(hydroxymethyl)methacrylamide, N-(hydroxyethyl)methacrylamide, N-(hydroxy propyl) methacrylamide, N-
(1,1-dimethyl-2-hydroxyethyl)acrylamide, N-(2,2-dimethyl-2-hydroxyethyl)methacrylamide, N-(1-ethyl-2-hydroxyethyl)methacrylamide, N-(1 , 1-dimethyl-3-hydroxypropyl) methacrylamide, N
- Monohydroxyalkyl (meth)acrylamide such as (1,1-dimethyl-3-hydroxybutyl)methacrylamide; N-Cl, 1-bis(hydroxymethyl)
Dihydroxyalkyl (meth)acrylamide such as ethylcoacrylamide, N,N-bis(2-hydroxyethyl)acrylamide, N-Cl, 1-bis(hydroxymethyl)ethyl]methacrylamide; N-(2-hydroxy-1, N such as trihydroxyalkyl (meth)acrylamide such as 1-bis(hydroxymethyl)ethylcoacrylamide, N-(2-hydroxy-1,l-his(hydroxymethyl)ethylcomethacrylamide)
-Hydroxyacrylamide or N-hydroxymethacrylamide is more preferably used.

In addition, the ethanolamine compound used preferably has the following general formula % formula % () (wherein R11t R11 is a hydrogen atom, carbon number 1 to 15
It is preferable to use an alkyl group or a CH,C)I, OH group. Specific examples of this compound include N-methylgetanolamine, N-H-converted ethylgetanolamine, N-7'lopyldiethanolamine, and N-octylgetanolamine.

In the ethanolamine compound represented by the general formula (V), when the number of carbon atoms in the N-[9furkyl group exceeds 16, the solubility in a solvent decreases.

The blending amount of the above compound in the crosslinkable resin material is 30 to 80 parts by weight of the polyfunctional monomer and 20 to 6 parts by weight of the monomer of general formula (I).
0 parts by weight, phosphoric acid ester monomer 1 of general formula (It)
~10 parts by weight, (Me,5')acrylamide compound 1~
51 parts by weight and 1 to 10 parts by weight of the ethanolamine compound (100 parts by weight in total).

Outside the above usage range, it becomes difficult to form a cured film with well-balanced abrasion resistance, antifogging properties, and antistatic properties.

To form a cured film on a synthetic resin substrate, the above-mentioned resin material is coated and cured. Coating methods include roll coating, brush coating, spray coating, and dip coating.

The coating film is cured using radiation such as α rays, β rays, γ rays, and electron beams or wavelengths of 2000 to 8000A+7.
) A light beam, particularly a light beam with a wavelength of 3000 to 5000 A, can be used. When a light beam is used as the active energy ray, it is necessary to include a photosensitizer in the resin and keep it at °C. Specific examples of these photosensitizers include benzoin, benzoin methyl ether, benzoin ethyl ether,
Examples include benzoin butyl ether, pentwinisopropyl ether, benzoinpropyl ether, benzyl, benzophenone, methylphenylglyoxylate, etc., and the amount of these used is based on the crosslinkable resin material 1
The amount is 0.01 to 10 parts by weight per 0.00 parts by weight, and if it is too large, the cured film may be colored.

In addition, the crosslinkable resin material used in the present invention can be used as is, but the coating workability when coating,
Organic solvents can also be added to improve coating uniformity and adhesion.

The organic solvent that can be added is not particularly limited as long as it can uniformly dissolve the crosslinkable resin material, such as ethyl alcohol, isopropyl alcohol, n-7
Alcohols such as ethyl alcohol; Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; Ketones such as aton, methyl ethyl ketone, and methyl isobutyl ketone; Ethers such as dioxane; ethyl acetate, n-butyl acetate・Esters such as inamyl acetate and ethyl propionate; polyhydric alcohol-conducting conductors such as ethylene glycol motuptyl ether, N, N-
Examples include dimethylformamide.

The amount of the organic solvent used can range from 95 to 10 parts by weight (total 100 parts by weight) based on 5 to 90 parts by weight of the crosslinkable resin material.

The thickness of the hardened film provided on the mirror surface is 0.5 to 100μ.
It is desirable to apply the coating in a range of m, preferably in a range of 1 to 50 μm.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, evaluation in Examples was performed using the method shown below.

(1) Attach abrasion-resistant #000 steel wool to the tip of a 25-diameter silk cylinder and bring it into contact with the horizontally placed sample surface (viewing surface).
The extent of scratches on the sample surface was visually observed when the sample was rotated 10 times under a 001 load.

(2) Anti-fog property - After holding the sample at a temperature of 20℃ for 5 minutes,
The sample was taken out at a constant temperature of 0° C. and relative humidity of 65%, and the time until dew condensation formed on the sample surface (viewing surface) was measured.

(3) Measurement of antistatic charge half-life After holding the sample at a constant temperature of 20°C and 65% relative humidity for 24 hours, a voltage of 10 KV was applied for 30 seconds using a static honest meter to measure the half-life. It was measured.

Example 1 Dipentaerythritol hexaacrylate was applied to one side of a 31m methacrylic resin plate on which aluminum was vacuum-deposited 40.
0% by weight tetrahydrofurfuryl acrylate)
10.0 #Polyethylene glycol #600
A crosslinkable resin material consisting of diacrylate 40.0% by weight acryloyloxyethyl phosphate 5.0N-(hydroxymethyl)acrylamide 2.0#N-octyljetanolamine 3.0#benzoin isopropyl ether 4.0# It was coated using a bar coater, and then the thickness of the coating (H-02L-2) made by Iwasaki Electric Co., Ltd. was 10
A sample having a diameter of μm was obtained.

The abrasion resistance of this abrasion-resistant methacrylic resin plate was tested using the test method described above, and the abrasion resistance was good with almost no scratches observed. As for anti-fogging properties, no dew condensation was observed on the surface of the cross-linked cured coating, and it had good anti-fogging properties. Regarding antistatic ability, the charge half-life was 1.0 seconds, and it had excellent antistatic ability.

Example 2 30.0L of dipentaerythritol pentaacrylate was applied to both sides of the three dragon polycarbonate resin plates on which aluminum was vacuum-deposited.
iSaturated polyester polyacrylate synthesized from 1% trimethylolethane, acrylic acid and succinic acid
10.0 #1.6-hexanethiol diacrylate) 12.0 #polyethylene glycol'+1ooo diacrylate 35.0
#Methacryloyloxyethyl phosphate 6.0
#N-(hydroxymethyl)acrylamide 3.0
#N-7' lobil diethanolamine 4.
0# Methyl phenyl glyoxylate 3.
5〃Isopropyl alcohol 120
．． 0 - toluene 3
Apply a crosslinkable resin material made of 0.0# by dipping method,
After sufficiently evaporating the organic solvent, a crosslinked cured film was formed under the same conditions as in Example 1. A film having a thickness of 4 microns was obtained. Next, aluminum was vacuum-deposited on one side of this resin plate to form a mirror. The abrasion resistance of this mirror was evaluated according to Example 1, and the abrasion resistance was good with almost no scratches observed. Good results were also obtained regarding anti-zero properties, and no dew condensation was observed on the surface of the crosslinked cured film. Regarding antistatic ability, the charge half-life was 1.5 seconds, and it had good antistatic ability.

Example 3 Dipentaerythritol hexaacrylate 18 on both sides of the methacrylic resin plate of Example 1
．． 5% by weight dipentaerythritol pentaacrylate 10.0 Dipentaerythritol tetraacrylate 10.0 2-hydroxyethyl acrylate 10. Ol polyethylene glycol #600 diacrylate 45.0 #
Acryloyloxyethyl phosphate 3.
0#N-(hydroxymethyl)acrylamide
2.0#N-laurylgetanolamine
1.51 benzoin ethyl ether
4. O Inbutyl alcohol
100.0 xylene
A crosslinkable resin material of 50.0# was applied by dipping, and after the organic solvent was sufficiently evaporated, a crosslinked cured film was formed in accordance with Example 1. A film thickness of 5 microns was obtained. Next, aluminum was vacuum-deposited on one side of this resin plate in the same manner as in Example 2 to form a mirror. This mirror had the following physical properties.

Abrasion resistance: No scratches observed. Anti-fogging property: No dew condensation. Antistatic property: Charge half-life: 2.0 seconds Comparative Examples 1 to 4 A cross-linked resin material made of one side of the methacrylic resin plate of Example 1 was brushed. A cross-linked cured film was formed using a high-pressure mercury lamp (irradiation conditions:
Same as Example 1). The film thickness of the coating is from 10 microns to 15 microns.
It had a micron.

Comparative Example 1 is a system that does not contain monomers with more than two functions,
Insufficient wear resistance. Comparative Example 2 is a system in which the monomer represented by general formula (1) is not blended, and although it has excellent abrasion resistance and antistatic properties, its antifogging performance is insufficient. ing.

Comparative Example 3 does not contain any bifunctional or higher functional monomer and is composed only of the monomer represented by general formula (I), and although it has excellent antifogging and antistatic properties, it has poor abrasion resistance. is insufficient.

Comparative Example 4 is a system in which general formula (1), hydroxyl group-containing acrylamide, and ethanolamine compounds are not blended, and although it has excellent abrasion resistance, antifogging and antistatic properties are insufficient. It is.

〔Effect of the invention〕

Synthetic resin mirrors with the above-mentioned structure have excellent abrasion resistance, anti-fogging properties, and antistatic properties, so
It can be widely used in household mirrors as well as vehicles.

Claims (1)

[Scope of Claims] A vacuum-deposited reflective film is formed on one side of a synthetic resin substrate, and (1) two or more acryloyloxy groups and/or methacryloyloxy groups in one molecule are formed on the other side of the synthetic resin substrate. 30-80% by weight of compounds having groups (2) The following general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R_1 is a hydrogen atom or a methyl group, and R_
2 is an alkoxy group, acryloyloxy group, or methacryloyloxy group having 1 to 5 carbon atoms, and n is 5 to 30
20 to 60 parts by weight of a monomer (which is an integer of R_
4 is a hydrogen atom or ▲There are mathematical formulas, chemical formulas, tables, etc.▼
group, R_5 is the same as R_3, m and n are 1 to 15
Phosphate ester monomers 1-
10% by weight (4) 1 to 5% by weight of hydroxyl group-containing acrylamide or hydroxyl group-containing methacrylamide and (5) 1 to 10% by weight of ethanolamine compound. Synthetic resin mirror.