JPS60184530A - Heat-resistant resin molding of excellent abrasion resistance and its production - Google Patents

Abstract

PURPOSE:To produce a heat-resistant, two-layer structure polymer of excellent abrasion resistance, by coating the surface of a specified resin molding with a specified resin material which can be cured by crosslinking and irradiating the surface with actinic energy rays. CONSTITUTION:A resin molding is produced by coating the surface of a resin molding comprising 2wt% or above N-substituted methacrylimide structure units of the formula (wherein R is a 1-20C alkyl or aryl) and 98wt% or below ethylenic monomer units (e.g., methyl methacrylate) with a resin material being curable by crosslinking and containing at least 30wt% monomer having at least three (meth)acryloxy groups in the molecule [e.g., trimethylolpropane tri(meth)- acrylate], and irradiating the surface with actinic energy rays to form a crosslinked and cured film on the surface of the resin molding. In this way, a resin polymer of a two-layer structure comprising a base of excellent heat-resistance and a coating layer which can form a crosslinked and cured film excellent in abrasion resistance, solvent resistance, surface smoothness, flexibility, and adhesion to the base can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing a heat-resistant polymer with excellent wear resistance.

In more detail, we need a coating layer that can form a crosslinked cured film with excellent abrasion resistance, surface smoothness, flexibility, 1lFI solvent resistance, durability, and adhesion to the substrate, and a substrate with excellent heat resistance. The present invention relates to a method for producing a resin polymer having a two-layer structure.

[Technology background]

(1) (In the formula, R represents an alkyl group or an aryl group consisting of 1 to 20 carbon atoms) 2% by weight or more of N-substituted methacrylimide represented by the structural formula (1) and 98% by weight of an ethylenic monomer % or less is thermoplastic and has excellent heat resistance.

However, the wear resistance of the surface is insufficient, and the surface may be damaged due to contact with other objects, impacts, scratches, etc. during transport, handling, or use of the molded product, resulting in reduced product yield. It may cause damage or detract from the aesthetic appearance.

Various methods have been studied to improve the inherent drawbacks of such synthetic resin molded products. There is a method in which a polymer is applied as a crosslinked coating material to the surface of a synthetic resin molded product, and active energy rays are irradiated to form a crosslinked cured film on the surface of the synthetic resin molded product by radical polymerization.

Conventionally, such polyfunctional (meth)acrylate (acrylate or methacrylate, hereinafter the same) monomer has excellent polymerization activity when irradiated with active energy rays, so it has been used as a quick-drying ink material in US Pat. No. 3,661,614; No. 35513i1, No. 3551'246@, British Patent No. 1198259, etc., and these polyfunctional (meth)acrylate monomers have been proposed as surface modifying materials for synthetic resin molded products. U.S. Pat. No. 35529 & 6, U.S. Pat.
3 or the specification of the same No. 3770490.

On the other hand, the present applicant and others have already discovered that a more polyfunctional (meth)acrylate monomer has excellent crosslinking and curing polymerizability upon irradiation with active energy rays, and that it improves the abrasion resistance of the surface of synthetic 4T4 resin molded products. We have discovered that it is effective as a material for cured films and have made many proposals. (For example, Special Publication No. 48-42211.49-12886, etc.).

However, the materials on which these cross-linked cured films are applied are mostly limited to general-purpose plastic substrates, and the current situation is that no consideration has been given to developing them into new substrates.

[Purpose of the invention]

An object of the present invention is to provide a resin polymer that maintains the heat resistance of a heat-resistant resin polymer base material or that maintains excellent abrasion resistance without impairing its heat resistance.

[Structure of the invention]

The heat-resistant resin polymer with excellent abrasion resistance of the present invention is a polymer resin base material consisting essentially of 2% by weight or more of N-substituted methacrylimide and 98% by weight or less of ethylenic monomer.
It is characterized by being provided with a cured coating of a crosslinked curable resin material containing 30% by weight or more of at least one monomer having three or more (meth)acryloyloxy groups in the molecule. It is something.

(Detailed Description of the Invention) To produce a heat-resistant resin polymer having excellent wear resistance according to the present invention (in ε, the base polymer substantially contains an N-substituted methacrylimide component) Thus, a heat-resistant resin was obtained that exhibited high heat-resistant moldability and mechanical properties that could not be achieved with conventional copolymer resins, and had excellent productivity.

By providing a cured coating of a cross-linked curable resin material made of a monomer having three or more (meth)acryloyloxy groups in one molecule on the surface of a heat-resistant resin base material with such excellent properties, we have achieved the level that we have achieved in the past. A resin polymer was obtained that had heat resistance and abrasion resistance that were previously unobtainable, and was well-balanced in various performances.

The heat-resistant resin base polymer of the present invention contains substantially 2% by weight or more of an N-substituted methacrylimide component and 98% by weight of an ethylenic monomer.
It is a polymer or copolymer consisting of less than or equal to %. Among the above components, the N-substituted methacrylimide component is a component necessary to maintain heat resistance and mechanical properties.

The N-substituted methacrylimide component is required to be 2mff1% or more. In order to expect clear heat resistance, it is preferable to have a heavy protein content of 10% or more.

If it is less than 2% by weight, the resulting polymer will have insufficient heat resistance.

One ethylenic monomer component is a component that maintains weather resistance, transparency, and mechanical properties.

The ethylenic monomer is preferably methyl methacrylate, but in addition to the methyl methacrylate component, a small amount of other components, preferably up to 20% by weight, such as methyl acrylate, ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate.

At least one component selected from benzyl methacrylate, methacrylic acid, acrylic acid, styrene, α-methylstyrene, etc. may be included.

In addition to these copolymer components, the following components may also be included.

For example, vinylbenzene, triallyl cyanurate, triallyl isocyanurate, ethylene glycol.

It may consist of one or more polyfunctional reactive monomers (A) such as dimethacrylate, 1-lyethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate.

To produce a heat-resistant resin base material, copolymerize a mixture consisting essentially of 2% by weight or more of N-substituted dimethacryamide and 98% by weight or less of methyl methacrylate, or 98% by weight or less of methyl methacrylate as the main component. It can be obtained by

To produce a heat-resistant resin-based oil, a radical polymerization catalyst is added to the mixture of the above-mentioned copolymerization components, and the resulting copolymerization mixture is first heated to a temperature of 50 to 1'80"C, preferably 65 to 130"C, and polymerized. After that, the polymerization is further heated at a humidity of 100 to 160°C for 30 to 180 minutes to complete the polymerization.

This method is the so-called 1311 polymerization method.

A cured film of a crosslinked curable resin material is provided on one surface of the heat-resistant resin polymer to produce a resin polymer with excellent wear resistance.

As the cross-linked curable resin material, various materials having cross-linked and curable groups in the molecule can be used, or cross-linked curable unsaturated resin materials can be used from the viewpoint of abrasion resistance, adhesion to plastic substrates, and transparency. 3 or more metabolites in one molecule as a group)
A crosslinked curable resin material containing 30% by weight or more of at least one monomer having an acryloyloxy group is preferred.

Compounds containing three or more acryloyloxy and/or methacryloyloxy groups in one molecule include trimethylolpropane 1-acrylate or trimethacrylate, 1-helimedyrollethane triacrylate or trimethacrylate, pentadarycerol triacrylate, Le-1- or trimethacrylate, pentaerythritol triacrylate or trimethacrylate, pentaerythritol tetraacrylate or de-1-ra methacrylate, dalycerin 1-lyacrylate or trimethacrylate, dipentaerythritol 1-lyacrylate or trimethacrylate,
dipentaerythritol acrylate or tetra methacrylate 1, dipentaerythritol 1 hel penta acrylate 1 or penta methacrylate, diventaerythritol hexaacrylate or hexa methacrylate tripentaerythritol te 1-lyacrylate or tetra Polyacrylates of polyhydric alcohols such as methacrylate, 1-repentaerythritol pentaacrylate or pentamethacrylate, tripentaerythritol hex-1-noacrylate or hexamethacrylate-1-, tripentaerythritol heptaacrylate-1- or heptamethacrylate-1- or polymethacrylate; Maron 1Ili/l-
Rimethy0-luethane/acrylic acid or methacrylic acid, malonic acid/trimethylolpropane/acrylic acid or methacrylic acid, malonic acid/glycerin/acrylic acid or methacrylic acid, malonic acid/pentaerythritol/acrylic acid or methacrylic acid, succinic acid/ Trimethylolethane/acrylic acid or methacrylic acid, succinic acid/trimethylolpropane/acrylic acid or methacrylic acid.

Kohaku l! i/glycerin/acrylic acid or methacrylic acid, succinic acid/pentaerythritol/acrylic acid or methacrylic acid, adipic acid/trimethylolethane/acrylic acid or methacrylic acid, adipic acid/trimethylolpropane/acrylic acid or methacrylic acid, adipic acid /pentaerythritol (・-) / acrylic or methacrylic acid, adipic acid / glycerin / acrylic or methacrylic acid, glutaric acid / trimethylolethane / acrylic acid or methacrylic acid, glutaric acid / trimethylolpropane / acrylic acid or methacrylic acid, glutaric acid acid/glycerin/acrylic acid or methacrylic acid, glutaric M/pentaerythritol/acrylic acid or methacrylic acid, sebacic acid/1~rimethylolethane/acrylic acid or methacrylic acid, sebacic acid/]~rimethylolpropane/acrylic acid or methacrylic acid Acid, sebacic acid/glycerin/・
'Acrylic acid or methacrylic acid, Sebacin M/pentaerythritol/acrylic acid or methacrylic acid, fumaric acid/trimethylolethane/acrylic acid or methacrylic acid, fumaric acid/trimethylolpropane/acrylic acid or methacrylic acid, Fumar M/glyrelin /Acrylic acid or methacrylic acid, fumaric acid/Pentaerythritol/
Acrylic acid or methacrylic acid, itaconic acid/trimethylolethane/acrylic acid or methacrylic acid, itaconic acid/trimedylolpropane/acrylic acid or methacrylic acid.

Itaconic acid/Pentaerythritol/Acrylic acid or methacrylic acid, Maleic anhydride/Trimedyloethane/
Saturated or unsaturated polyester polyacrylates or polymethacrylates with combinations of compounds such as acrylic acid or methacrylic acid, maleic anhydride/glycerin/acrylic acid or methacrylic acid: trimedylolpropane toluylene diisocyanate-1-, or the following general A polyisocyanate represented by the formula.

CO (wherein R is hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), isoborone diisocyanate, or 1]limethylhexylylene diisocyanate.) Acrylic monomers having active hydrogen and polyisocyanates such as, for example, 2-hydroxyedyl acrylate or methacrylate, 2-hydroxypropyl acrylate or methacrylate,
2-Hydroxy-3-methoxypropyl acrylate-1-
Or urethane acrylate obtained by reacting 1 to methacrylate, N-methylolacrylamide or methacrylamide, N- with droxyacrylamide or methacrylamide, etc. in a quantity of 3 moles or more per isocyanate molecule by a dilute method: Others: tris + 2-hydroxyethyl Examples include triacrylate of isocyanuric acid and trimethacrylate.

In addition, as a monomer having three or more (meth)acryloyloxy groups in one molecule, in the following general formula, n is 1 to 4.
is a positive integer, and at least three of X are CH2=
Cf-I -C,OO- group or CH2=C(CH3)
It is a Coo- group, and the rest are -OH groups. ) It is particularly preferable to use a compound represented by the following.

Specific examples of the monomer represented by general formula (I) include dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol l-hexane. (Meta)acrylate, 1
- dipentaerythritol tri(meth)acrylate,
Examples include 1 helipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol 1 hex(meth)acrylate, etc., but these monomers contain nitrogen, argon, etc. It is particularly preferable because it can be easily cured by irradiation with active energy rays in normal air, not in an inert gas atmosphere, and can form a coating with excellent wear resistance.

Furthermore, when a crosslinked curable resin material made of these monomers is used, a crosslinked cured film with excellent smoothness and uniform thickness can be obtained, making it easy to produce a plastic cured film with a smooth surface. be able to. Furthermore, since the cured film made of the crosslinked curable resin material has excellent adhesion to the base plastic, there is no possibility that the film will peel off during use.

Other monomers that can be used in combination with monomers having three or more (meth)acryloyloxy groups in one molecule include monomers having two or less (meth)acryloyloxy groups in one molecule. Monomers having, for example, 2,2-bis(4-acryloxydie I~xyphenyl)propane, 2,2-bis(4-methacryloxyethoxyphenyl)propane, diethylene glycol di(meth)acryle-I~, Triethylene glycol di(meth)acrylate, tetraethylene glycol dimethacrylate, 2-
To hydroxyethyl (meth)acrylate-1.

Tetrahydrofurfuryl (meth)acrylate.

Examples include ethyl ruby (meth)acrylate. One or more of these monomers (6) are selected and used in an amount of up to 70% by weight of the crosslinked curable resin.

In order to provide a tightly adhered cured film of cross-linked curable resin with a film thickness of about 1 to 30 μm on the surface of the heat-resistant resin polymer base material, the cross-linked curable resin material is applied to the heat-resistant resin polymer base material. It is desirable to apply the coating to the areas requiring coating by a known method such as spray coating, casting coating, or dip coating, and then to avoid crosslinking and curing by irradiation with active energy rays.

As active energy rays, electron beams, ultraviolet rays, etc. can be used, but it is advantageous to use ultraviolet rays in terms of workability and ease of handling. When using ultraviolet rays as active energy rays, it is preferable to add a photoinitiator and/or photosensitizer to the crosslinked curable resin material.

The polyfunctional acrylate represented by the general formula (IF) has the following general formula (■): group, alkylene group, or substituted 7 group*
L/n11 T: Yes, nl, +12. n3.
114゜ml, m2. m3 and m4 take a numerical value of 0.1 or 2, and x is a positive integer from 1 to 10. ), for example, malonic acid/trimethylolethane/acrylic acid, malonic acid/trimethylolpropane/acrylic acid, succinic acid/1-rimethylolethane/
Acrylic acid, succinic acid/trimethylolpropane/acrylic acid, adipic acid/1-dimethylolethane/acrylic acid, or acibic acid/l~rimethylolpropane/
Esterification reaction products synthesized from a combination of compounds such as acrylic acid, and compound (■)/compound (Ili)-5~
When used together in a ratio of 115, the weather resistance of the molded article 1q is particularly preferred, especially since it prevents changes in appearance such as rough skin, cracks, peeling of the film, and poor adhesion due to accelerated exposure and natural exposure.

〔Effect of the invention〕

The heat-resistant polymer with excellent wear resistance of the present invention has smoothness,
It also has excellent chemical resistance and durability.

Fields where heat-resistant resin polymers with high abrasion resistance are required, such as CRT filters, television filters, taxi meters, digital display boards, and other displays, illumination optics, and fluorescent display tube filters. In addition to applications such as liquid crystal filters, it can also be used as a cover for automobiles, and therefore has extremely high industrial significance and value as a product that can respond to advances in car electronics.

The features and effects of the present invention as described above will be further explained by examples.

The measurements and evaluations in Examples a) were carried out in the following manner.

(1) Abrasion resistance a) Surface hardness Pencil hardness according to JIS K5651-1966 b) Scratch test Scratch test with #OOO sudir wool ○ - Even if lightly rubbed, the surface hardly gets scratched.

8- If you rub it lightly, the surface will be slightly scratched (.

X - Light scratching will cause severe scratches on the surface.

(Same level as the base resin) (2) Cross-cut cellotape peel test for adhesive crosslinked cured film. That is, make 100 scales of 1 mm2 by placing 11 film cutting lines vertically and horizontally on the film that reach the base material at 1 mm intervals, then stick cellophane tape on the scale and peel it off rapidly.

Repeat this cellotape operation three times at the same location.

○ - No peeling of cross-linked cured film even after repeating 3 times.

Δ-Number of peeling lines after repeating 3 times: 1 to 50 g.

×-Number of peeling stitches after repeating 3 times: 51 to 100.

(3) Surface smoothness measurement - The smoothness of the coated surface is very good and can be said to be a mirror surface.

Δ - The coating surface has good smoothness, but there are subtle disturbances and it cannot be said to be a mirror surface.

×- Surface is disturbed and smoothness is poor.

Example 1 Methyl methacrylate 5500ar (55 parts by weight), N-methyl dimethacrylamide 4500'or (45 parts by weight)
After putting tert-dodecyl mercaptan 10 (Ir) into a reaction vessel equipped with a cooling tube, a hygrometer, and a stirring bar, the mixture was heated with stirring to produce 2.21-azobis-(2,4-dimethyl) at an internal temperature of 70°C. Valeronitrile (0.5 g) was added and the internal temperature was maintained at 95 to 110° C. for 10 minutes.The reaction mixture was then cooled to air temperature to obtain a silubular partial polymer.

This partially polymerized product was made of polytetrafluoroethylene with 0.1
tert-dodecyl mercaptan per 100 parts by weight of the purified product obtained by filtering and purifying it with a μ filter.
．． After adding and dissolving 3 parts by weight and 0.3 parts by weight of lauroyl peroxide, 3 m was added through a polyvinyl chloride gasket.
A thermal lightning pair was set in a cell formed by two tempered glass plates facing each other at an interval of m, and the above composition was injected into the cell and immersed in warm water at 80°C to polymerize and harden.

The time from immersion in hot water until the internal temperature reached its peak (curing time) was measured, and 30 minutes after reaching the peak temperature, it was taken out of the hot water and then heat treated in an air heating oven at 120°C for 2 hours. .

After cooling, the cells were removed and the resulting resin plate with a thickness of about 6 mm was crushed in a clean box to obtain a core component polymer. The resulting resin polymer had Ml (230°C, load 3.8K(1)) of 3.5, refractive index of 1.530, specific gravity of 1.210, and heat distortion temperature of 152°C.

Next, this polymer was extruded using a 25φ vented extrusion die (Daiichi Jitsugyo (body die temperature: 230°C, adapter temperature: 230°C, screw barrel temperature: 200-230°C, full-flight screw L/D = 24). After molding, it was pelletized. Using this pelletized polymer, a 1-ounce vertical screw complete injection molding machine (Yamae Sei is a newly manufactured SAV 3
0A> heat resistant flat molded plate <80X80X2mm)
I got it. The surface hardness was 2H in terms of pencil hardness. A scratch test with steel wool showed that the surface was severely scratched when lightened.

30 parts of dipentaerythritol pentaacrylate, 30 parts of dipentaerythritol hexaacrylate, 20 parts of dipentaerythritol tetraacrylate, 2
- A cross-linked curable resin material consisting of 20 parts of hydroxyethyl acrylate and 4 parts of benzoin ethyl ether is uniformly coated on the resin molded plate by dip coating using 200 parts of isopropanol-toluene (6/4) 1 mixture. The material was then cured by irradiation with ultraviolet light emitted from a high-pressure mercury lamp.

The thus obtained heat-resistant resin plate, which has a cross-linked cured film of approximately 3μ on its surface, showed excellent abrasion resistance with almost no scratches even when an abrasion resistance test was performed using #OOO steel wool. It is.

Further, this crosslinkable cured film was extremely hard and had excellent adhesion to the base material, and the cross-cutting to sellotape peeling test was extremely good.The smoothness of the film was extremely good and mirror-like.

Example 2 A copolymer consisting of 60 parts by weight of methyl methacrylate, 20 parts by weight of styrene, and 20 parts by weight of N-methyldimethacrylamide was produced by the method of Example 1.

The resulting polymer had an Ml of 4.5, a refractive index of 1.515, a specific gravity of 1.200, and a heat distortion temperature of 130°C. Example 1
A resin flat plate was obtained in the same manner as above. The surface hardness was 1 on the pencil hardness scale. Results of V scratch test i with steel wool,
A light scratch caused severe scratches on its surface.

The crosslinked curable resin 4Δ material of Example 1 was used and cured by irradiation with ultraviolet rays emitted from a high-pressure mercury furnace.

The thus obtained heat-resistant resin plate having a cross-linked cured film of about 3 μm on its surface showed almost no scratches when subjected to an abrasion resistance test using #OOO steel wool, and had a pencil hardness of 7H.

Furthermore, the cross-linked cured coating was extremely hard and had excellent adhesion to the base material, and the cross-cut cellophane tape peel test was extremely good, and the coating had an extremely good mirror-like smoothness.

Example 3 After using the polymer of Example 1 as it was to prepare a flat molded plate by the method according to Example 1, 10 parts of dipentaerythritol pentaacrylate were added to dipentaerythritol, 10 parts of chiraacrylate, 8 parts of tetrahydrofurfuryl acrylate. part succinic acid 1
Mol/2 moles of trimethylolethane/4 moles of acrylic acid reacted ester 7 parts isopropyl alcohol
35 parts toluene 30 parts 2-hydroxy 2-methyl 1-phenylpropane-1
-On 2 parts Silicone leveling agent After it was uniformly applied by dip coating into a crosslinked curable resin material solution consisting of 6.2 parts, it was cured by irradiation with ultraviolet rays emitted from a high-pressure mercury lamp. The heat-resistant resin plate prepared in this manner was excellent in wear resistance, adhesion, and smoothness.

Example 4 N-methyldimethacrylamide 100 in Example 1
A heat-resistant resin polymer was produced using the same recipe as in Example 1 except that the parts by weight were changed.

MI of the obtained polymer (230°C, load 3.8K (1
>6.5, refractive index 1.532, specific gravity 1.325, and heat distortion temperature 168°C.

A flat molded plate was prepared by the method according to Example 1, and then coated uniformly by dip coating in the crosslinked curable resin material solution used in Example 3, and then exposed to ultraviolet light emitted from a high-pressure mercury lamp. hardened.

The resin body thus obtained was excellent in both heat resistance, abrasion resistance, adhesion and smoothness.

Attorney Akira Asamura Proceedings June 7, 1980 Commissioner of the Japan Patent Office 1, Indication of the case 1982 Patent Application No. 39412 Molded article and its manufacturing method 3, Person making the amendment Relationship with the case Waiting. ``Applicant 4, Agent 5, Daily Showa Order for Amendment 6, Number of inventions increased by the amendment 7, Detailed explanation of the invention in the specification subject to the amendment 8, Contents of the amendment as shown in the attached sheet (1) In the 13th line from the bottom of page 7 of the specification, add the following statement on a new line after "sufficient."

"The N substituent in the methacrylimide component of structural formula (1) must consist of C~02° saturated and unsaturated aliphatic and aromatic groups or mixtures thereof.

From the viewpoint of improving heat resistance, it is preferable that the chain length of the substituent is relatively short. Methyl p-ethyl, propyl.

Claims (2)

[Claims] (1) Structural formula: (wherein R represents an alkyl group or noaryl group having 1 to 20 carbon atoms) Crosslinking consisting of containing at least 30% by weight of at least one type of monomer having 3 or more (meth)acryloyloxy groups in one molecule on the surface of a resin molded product consisting of 98% by weight or less of matrix units. A heat-resistant resin molded product with excellent wear resistance, consisting of three hardened coatings of hardening resin material. (2) Structural formula: (wherein, R represents an alkyl group or an aryl group having 1 to 20 carbon atoms)
On the surface of a resin molded product consisting of the above and ethylenic monomer units with a monomer unit of 98% or less, three or more (meta)
After applying a crosslinked curable resin material containing 30% by weight or more of at least one type of monomer having an acryloyloxy group, active energy rays are irradiated to form a crosslinked cured film on the surface of the resin molded product. This is an ill manufacturing method for IC heat-resistant synthetic resin molded products with excellent wear resistance.