JPS60170634A - Molded article of heat-resistant resin having improved abrasion resistance and production thereof - Google Patents

Abstract

PURPOSE:A molded article having very high heat and abrasion resistance and further various improved performances, by forming a cured coat of a curable resin consisting of an acryloyloxy or methacryloyloxy group-containing monomer on the surface of a base material of a resin containing methacrylic acid anhydride. CONSTITUTION:A cured film of a crosslinking curable resin containing >=30wt% at least one of monomer having 3 or more (meth)acryloyloxy groups in 1mol is formed on the surface of a molded resin article consisting of >=2wt%, preferably >=10wt% methacrylic acid anhydride structural units expressed by the formula and <=98wt%, preferably <=90wt% ethylenic monomer units. The coat is obtained by irradiating a film coated by spray coating, etc. with active energy rays to crosslink and cure the film to about 1-30mu coat thickness.

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, solvent resistance, durability, and adhesion to the substrate, and a base with excellent heat resistance. The present invention relates to a method for producing a resin polymer having a 2B structure as a material.

[Technology/background]

l-13 The polymer represented by structural formula (1) consisting of 2% or more of methacrylic anhydride and 98% or less of ethylenic monomer is thermoplastic and has excellent heat resistance properties. .

However, the wear resistance of the surface is insufficient, and the surface may be damaged or droplets may drop due to contact with objects, impacts, scratches, etc. during transportation, handling, or use of the molded product. It may rust or the aesthetic appearance may be damaged.

Various methods have been studied to improve the inherent drawbacks of such synthetic resin molded products. For example, polyfunctional acrylates or methacrylates containing two or more polymerizable ethylenically unsaturated groups in one molecule There is a method in which a cross-linked and cured polymerizable monomer is applied to the surface of a synthetic resin molded article, and active energy rays are irradiated to form a cross-linked cured film on the surface of the synthetic resin molded article by radical polymerization.

Conventionally, such polyfunctional (meth)acrylate (acrylate-1 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 the US patent application. 3661614
No. 3551311, No. 3551246, British Patent No. 1198259, etc.
Regarding the application of these polyfunctional (meth)acrylate monomers as surface modifying materials for synthetic resin molded articles, see US Pat. No. 3,552,986, US Pat. No. 2,413,973 or US Pat. Proposed.

On the other hand, the present applicants have also discovered that a more polyfunctional (meth)acrylate monomer has excellent crosslinking and curing polymerizability upon irradiation with active energy rays, and that it can be crosslinked and cured to improve the abrasion resistance of the surface of synthetic resin molded products. We have discovered that it is effective as a membrane material and have made many proposals. (For example,
-42211.4, 9-12886, etc.).

However, the materials on which these crosslinked cured films are applied are mostly limited to general-purpose plastic substrates, and development to new substrates is limited to 1. The current situation is that it has not been considered.

[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 the heat resistance.

[Structure of the invention]

The heat-resistant resin polymer with excellent abrasion resistance of the present invention is a polymer resin that substantially consists of 2% or more of methacrylic anhydride and 98% or less of ethylenic monomer. 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. be.

[Detailed description of the invention]

In producing the heat-resistant resin polymer with excellent wear resistance of the present invention, the base polymer is characterized in that it substantially contains a methacrylic anhydride component, which cannot be achieved with conventional copolymer resins. A heat-resistant resin was obtained that exhibited higher heat-resistant moldability and mechanical properties than ever before, 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 methacrylic anhydride component and 98% by weight of ethylenic monomer.
It is a polymer or copolymer consisting of the following. Among the above components, the methacrylic anhydride component is a component necessary to maintain heat resistance and mechanical properties.

The amount of methacrylic anhydride component is required to be 2% by weight or more. In order to expect clear heat resistance, the content is preferably 10% by weight 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 a small amount of other components, preferably 20% by weight or less, is present in addition to the methyl methacrylate component, 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.

dimethacrylate, triethylene glycol]-dimethacrylate-1, trimethylolpropane trimethacrylate-1
- It may consist of one or more selected from polyfunctional reactive monophyles such as.

To produce heat-resistant resin materials, a polymer consisting of methacrylic acid and tert-butyl methacrylate, which are reaction precursors to produce a methacrylic anhydride component, and a copolymer such as methyl methacrylate containing these reaction precursors are used. Alternatively, the desired methacrylic anhydride polymer can be obtained by subjecting a copolymer containing the aforementioned other components to a thermal condensation reaction.

The heat treatment temperature for producing the methacrylic anhydride component of the present invention is 100°C or higher, particularly 130 to 450°C, preferably 150 to 300°C, and nitrogen, argon, etc. are used to prevent abnormal reactions. The heat treatment is preferably carried out in an autoclave under an inert gas atmosphere. It is also possible to add a thermal deterioration inhibitor such as an antioxidant to prevent thermal deterioration of the polymer during this heating reaction.

The antioxidants mentioned here include phosphite-based antioxidants, hindered phenol-based antioxidants, sulfur-based antioxidants, and amine-based antioxidants.

Phosphite-based antioxidants are represented by phosphite esters, and include tricresyl phosphite, cresyl phenyl phosphite, tributyl phosphite, and tributoxyethyl phosphite.

Examples of hindered phenolic antioxidants include hydroquinone, cresol, and phenol derivatives.

Examples of sulfur-based antioxidants include alkyl mercaptans and dialkyl disulfide derivatives.

Examples of amine-based antioxidants include naphthylamine, phenylenediamine, and hydroquinoline derivatives.

To prepare the polymer which is raw material 1 for obtaining the methacrylic anhydride component described above, conventional radical polymerization methods, ionic polymerization methods, etc. can be used, but radical polymerization methods are preferred from the viewpoint of productivity.

The polymerization catalyst used to obtain the above polymer is, for example, azobisisobutylonitrile, 2,2'-azobis-(
From azobis-based catalysts such as 2,4-dimethylvaleronitrile), diacyl peroxide-based catalysts such as lauroyl peroxide, benzoyl peroxide, bis(3,5゜5-1-rimedylhexanoyl) peroxide, and Bell Carbone 1-based catalysts, etc. You can choose.

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

As the cross-linking curable resin material, various materials having cross-linking and curable groups in the molecule can be used. As a basis, 3 or more molecules per molecule (meta)
At least one monomer having an acryloyloxy group
A cross-linked curable resin material containing 30% by weight or more of seeds is preferred.

Examples of compounds having three or more acryloyloxy and/or methacryloyloxy groups in one molecule include trimethylolprobant acrylate or trimethacrylate, trimethylolethane triacrylate or trimethacrylate, pentadalicerol triacrylate or] helimethacrylate, pentaerythritol triacrylate or trimethacrylate,
Pentaerythritol tetraacrylate or tetramethacrylate, glycerin triacrylate or trimethacrylate, dipentaerythritol triacrylate or trimethacrylate, dipentaerythritol tetraacrylate or tetramethacrylate, dipentaerythritol pentaacrylate or pentamethacrylate, dipentaerythritol hexaacrylate or Polyacrylates or polymethacrylates of polyhydric alcohols such as hexamethacrylate tripentaerythritol tetraacrylate or tetramethacrylate, tripentaerythritol pentaacrylate or pentamethacrylate, tripentaerythritol hexaacrylate or hexamethacrylate, tripentaerythritol hexaacrylate or heptamethacrylate; Malonic acid/trimethylolethane/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 Acid/trimethylolethane/acrylic acid or methacrylic acid, succinic acid/
Trimethylolpropane/acrylic acid or methacrylic acid.

succinic acid/glyrelin/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 acid or methacrylic acid, Adipic acid/glycerin/acrylic or methacrylic acid, glutaric acid/trimethylolethane/acrylic or methacrylic acid, glutaric acid/trimethylolepropane/acrylic or methacrylic acid, glutaric acid/glycerin/acrylic or methacrylic acid, glutaric acid /Pentaerythritol/Acrylic acid or methacrylic acid, Sebacin II
/ trimethylolethane / acrylic acid or methacrylic acid, sebacic acid / trimethylolpropane / acrylic acid or methacrylic acid, sebacic acid / glycerin / acrylic acid or methacrylic acid, sebacic acid / pentaerythritol / acrylic acid or methacrylic acid, fumaric acid / Trimethyllolethane/acrylic acid or methacrylic acid, fumaric acid/trimethylolpropane/acrylic acid or methacrylic acid, fumaric acid/glycerin/acrylic acid or methacrylic acid, fumaric acid/pentaerythritol/acrylic acid or methacrylic acid, itacon Acid/trimethylolethane/
Acrylic acid or methacrylic acid, itaconic acid/trimethylolpropane/acrylic acid or methacrylic acid.

Itaconic acid / Pentaerythritol / Acrylic acid or methacrylic acid, Maleic anhydride / Trimethylolethane /
Saturated or unsaturated polyester polyacrylate or polymethacrylate made from a combination of compounds such as acrylic acid or methacrylic acid, maleic anhydride/glycerin/acrylic acid or methacrylic acid; trimethylolpropane toluylene diisocyanate, or a polyester having the following general formula: Isocyanate.

GO (wherein R is hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), isoborone diisocyanate or trimethylhexamethylene diisocyanate). Acrylic monomers containing isocyanate and active hydrogen, such as 2-hydroxyethyl acrylate or methacrylate, 2-hydroxy 7oivir acrylate or methacrylate,
2-Hydroxy-3-methoxypropyl acrylate or methacrylate, N-methylolacrylamide or methacrylamide, N-hydroxyacrylamide or methacrylamide, etc. as isocyanate 1
Urethane acrylate obtained by reacting 3 moles or more per molecule by a conventional method; other examples include triacrylate or trimethacrylate of tris+2-hydroxyethyl+isocyanuric acid.

In addition, as a monomer having three or more (meth)acryloyloxy groups in one molecule, the following general formula (where n is 1 to 4
is a positive integer, and at least three of X are CH2=
CH-Coo- group or haCl-12=C(C)-13)C
oo-mT-, and the rest are -o1'' groups. ) It is particularly preferable to use a compound represented by the following.

Specific examples of the monomer represented by general formula (n) include dipentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa (meth)acrylate, tripentaerythritol tri(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, etc. The monomer is particularly preferred because it can be easily cured by irradiation with active energy rays in ordinary air, not under an inert gas atmosphere such as nitrogen or argon, 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 the monomer having three or more (meth)acryloyloxy groups in one molecule include monomers having two or more (meth)acryloyloxy groups in one molecule. A monomer having, for example, 2.2-
Bis(4-acryloxyjethoxyphenyl)propane, 2,2-bis(4-methacryloxyethoxyphenyl)propane, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acryle, -
G, Te1 - Ethylene glycol dimethacrylate, 2
-Hydroxyethyl (meth)acrylate.

Examples include tetrahydrofurfuryl (jri)acrylate 1, edylcarbitol (meth)acrylate, and the like.

One or more of these monomers are selected and used in the crosslinked curable resin material in an amount of 70% or less.

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 coated on the surface of the heat-resistant resin polymer base material. It is desirable that the coating be applied to the areas requiring painting by a known method such as spray coating, casting coating, or dip coating, and then cross-linked and cured 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 (II) has the following general formula (■): (CI-12) -R 2 (CH2)n3-R (CH2)m3R (wherein at least three R are CI -12=C,l-1-CO0- group, the remainder is -H1 hydroxyl group, amino group, alkylene group, or substituted alkylene group, nl, n2.n3.n4゜ml, m2.m3 and ll14 takes a value of 0.1 or 2, and X is a positive integer from 1 to 10.) Compounds represented by, for example, malonic acid/trimethylolethane/acrylic acid, malonic acid/trimethyl Methylolpropane/acrylic acid, succinic acid/trimedylolethane/acrylic acid, succinic acid/trimedylopropane/acrylic acid, adipic acid/trimethylolethane/acrylic acid, or adipic acid/trimethylolpropane/acrylic acid, etc. Esterification reaction product etc. synthesized from the combination of compounds and compound (■)/compound (III)-5 to 11
When used at a ratio of 5 to 71, it is particularly preferable because it prevents the weather resistance of the resulting molded product, especially 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 excellent abrasion resistance are required, such as CRT filters, TV filters, taxi meters, digital display boards, and other display-related lighting optical-related products, fluorescent display tube filters, liquid crystal products, etc. In addition to applications such as filters, it can be used as headlight covers for automobiles, and therefore has extremely high industrial significance and value as it can respond to the development of car electronics.

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

Note that the measurement and evaluation in the examples were performed in the following manner.

(1) Abrasion resistance a) Surface hardness Pencil hardness according to JIS K5651 b) ffX (El test #OOO steel wool abrasion test 〇 - Even a light touch will hardly scratch the surface.

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

X - Light rubbing will severely scratch the surface.

(Same level as the base resin) (2) Cross-cut cellotape peel test for adhesive crosslinked cured film. That is, make 100 1 mm2 scales by cutting 11 film cutting lines vertically and horizontally at 1 mm intervals on the film, and then apply cellophane tape to 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 stitches after repeating 3 times: 1 to 50.

×-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 0.751 t e +' t dodecyl mercaptan per 100 parts by weight of methacrylic ffi tart-butyl
After melting and adding 1 part of azobisbutyronitrile and 0.4 parts by weight of azobisbutyronitrile, a thermocouple was set in a cell formed by two tempered glass plates facing each other at a distance of 3 mm through a polyvinyl chloride gasket. Inject the above monomer solution into 8
It was immersed in warm water at 0°C to polymerize and harden. Thirty minutes after the internal temperature reached a peak after being immersed in hot water, it was taken out from the hot water and then heat treated in an air heating furnace at 120°C for 2 hours.

After cooling, the cell was removed and the resulting resin plate with a thickness of 6m+n was crushed in a clean box. Antige Bl-IT (2.6 di-tert-butyl-P-cresol manufactured by Kawaguchi Chemical Industry Co., Ltd.) was added to 100 parts by weight of this polymer.
0.01 parts by weight was charged into a 3-volume autoclave, and nitrogen purging was repeated and the mixture was heated and reacted in an oil bath at 250° C. for 4 hours to obtain a transparent resin polymethacrylic anhydride polymer.

From the infrared absorption spectrum, it is 18020m-1,1760
An absorption peculiar to methacrylic anhydride was observed at cm-1.

MI of i4J polymer (230°C load 3.81
g) is 4.01, refractive index 1.52+6, specific gravity 1.303
, at a heat distortion temperature of 170°C.

Next, this polymer was extruded using a 25φ vented extruder (Daiichi Jitsugyo 6-gradient die temperature 230°C, adapter temperature 230°C, screw barrel temperature 200-230°C full-flight screw L/D = 24). The pelletized polymer was extruded into pellets.The pelletized polymer was used to prepare a 1 oz.
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 dipenta 1 lythritol pentaacrylate, 830 parts of dipentaerythritol hexaacrylate, 20 parts of dipentaerythritol tetraacrylate, 2
- A cross-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) mixed solvent. The material was then cured by irradiating it with ultraviolet light emitted from a high-pressure water tank.

The thus obtained heat-resistant resin plate, which has a cross-linked hardness of about 3 μm on its surface, showed excellent abrasion resistance with almost no scratches even when an abrasion resistance test was performed using #OOO steel wool. be.

Further, this crosslinkable cured film was extremely hard and had excellent adhesion to the substrate, and the cross-cut Sellotape peel test was extremely good.The smoothness of the film was extremely good and mirror-like.

Example 2 50 parts by weight of methyl methacrylate, tert methacrylate
A copolymer was obtained in the same manner as in Example 1 with a monomer composition of -butyl of 50 parts by weight. A methyl methacrylate-methacrylic anhydride copolymer was obtained by heating reaction in an autoclave using 0.011) m part of Antige BHT per 100 parts by weight of the obtained polymer. The acid anhydride conversion rate was 42% from the infrared absorption spectrum. MI of the obtained polymer
(230℃, load 3.8Kg) is 5.5, refractive index 1.5
04, specific gravity 1.235, and heat distortion temperature 141°C.

A resin flat plate was obtained in the same manner as in Example 1. The surface hardness was 1 on the pencil hardness scale. A steel wool abrasion test showed that the surface was severely scratched when lightly rubbed.

The crosslinked curable resin 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 approximately 3 μm on its surface showed almost no scratches even when subjected to an abrasion resistance test using #OOO steel wool, and had a pencil hardness of 7H.

Further, the cross-linked cured film was extremely hard and had excellent adhesion to the substrate, and the cross-cut Sellotape peel test was generally good, and the film had an extremely good mirror-like smoothness.

Example 3 A methacrylic anhydride polymer was obtained in the same manner as in Example 1, using the polymer of tert-butyl methacrylate of Example 1 as it was.

After producing a flat molded plate by the method according to Example 1, 10 parts dipentaerythritol pentaacrylate 1-10 parts dipentaerythritol hexaacrylate 8 parts tetrahydrofurfuryl acrylate 1 part succinic acid
7 parts isopropyl alkyl, an ester obtained by reacting mol/2 mol of trimethylolethane/4 mol of acrylic acid
35 parts toluene 30 parts 2-hydroxy 2-methyl 1-phenylpropane-1
-A 2 parts Silicone leveling agent After it was uniformly applied by dip coating into a solution of a crosslinked curable resin material 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 thus obtained was excellent in abrasion resistance, adhesion, and smoothness.

Example 4 A copolymer was obtained in the same manner as in Example 1 using a monomer composition consisting of 3-0 parts of methyl methacrylate, 20 parts of styrene, 10 parts of methacrylic acid, and 40 parts of tert-butyl methacrylate. Thereafter, a polymer containing methacrylic anhydride was obtained in the same manner as in Example 1.

A flat molded plate was prepared by the method according to Example 1, and then uniformly coated by dip coating in the crosslinked curable resin material solution used in Example 3, and then cured by irradiation with ultraviolet rays emitted from a high-pressure mercury lamp. I let it happen.

The resin body prepared in this manner was excellent in both heat resistance, abrasion resistance, adhesion and smoothness.

Agent Asamura Hako

Claims (2)

[Claims] (1) Structural formula: On the surface of a resin molded product consisting of 2% by weight or more of methacrylic anhydride structural units and 98% by weight or less of ethylenic m-units, three or more (meth) ) A heat-resistant resin molded article with excellent abrasion resistance, which is provided with a cured coating of a crosslinked curable resin material containing 30% by weight or more of at least one type of monomer having an acryloyloxy group. (2) Structural formula: 3 or more ( After applying a cross-linked curable resin material containing at least 30% by weight of at least one monomer having a meth)acryloyloxy group, the surface of the resin molded article is cross-linked and cured by irradiation with active energy rays. A method for producing a heat-resistant synthetic resin molded product with excellent wear resistance, which is characterized by forming a film.