JPS60190428A - Molded article of heat-resistant resin having improved abrasion resistance and production thereof - Google Patents

Abstract

PURPOSE:A molded article, obtained by forming a cured film of an acryloyloxy group-containing resin on the surface of a polymer base material consisting of an N-substituted methacrylimide and an ethylenically unsaturated monomer, having improved heat resistance and high productivity, and capable of exhibiting improved abrasion resistance. CONSTITUTION:A molded article obtained by applying a crosslinkable curable resin material containing >=30wt% at least one monomer having three or more (meth)acryloyl groups in one molecule to the surface of a molded article of a resin consisting of >=2wt%, preferably >=10wt% N-substituted methacrylimide structural units expressed by the formula (R is 1-20C alkyl or aryl) and <=98wt % ethylenic monomer, and irradiating the resultant film with active energy rays to form a crosslinked cured film thereon. Methyl group is preferred for the 1-20C alkyl group in the methacrylimide component. The ethylenic monomer contains preferably >=80wt% methyl methacrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for manufacturing a 7j heat-resistant handcart body 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 substrate with excellent heat resistance. The present invention relates to a method for producing a resin polymer having a two-layer structure.

(In the formula, R represents an alkyl group or an aryl group having 1 to 20 carbon atoms) 62% or more of the N-substituted methacrylic compound represented by the structural formula (1) and 98% by weight of ethylene l'l monomer The polymer consisting of the following is thermoplastic and has excellent heat resistance properties.

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 transportation of molded products, handling of parts, or use, resulting in reduced product accumulation. It may look rough and the aesthetic appearance may be damaged.

Various methods have been investigated to improve the inherent drawbacks of such synthetic resin molded products. 1. There is a method in which a monomer is applied as a crosslinked cured coating material to the surface of a synthetic resin molded product, and a crosslinked cured film is formed on the surface of the synthetic resin molded product by radical polymerization using active energy rays. .

Conventionally, such polyfunctional (meth)acrylate (acrylate or methacrylate monomer, hereinafter the same) monomer has been granted a U.S. patent as a material for quick-drying inks because of its excellent polymerization activity when exposed to active energy rays. No. 3661614
No. 3551311, No. 3551246@, and British Patent No. 1198259, the use of these polyfunctional (meth)acrylate monomers as a surface-modifying material for synthetic resin molded articles has been proposed. Applications are proposed in US Pat. No. 3,552,986, US Pat. No. 2,413,973, and US Pat. No. 3,770,490.

On the other hand, the present applicant and others 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 improves the abrasion resistance of the surface of synthetic resin molded products and is capable of crosslinking and curing. We have found that it is effective as a membrane cover and have made many proposals. (For example, Tokuko Sho 4-
8-42211.49-12886, etc.).

However, the material on which these crosslinked cured films are provided is in most cases general-purpose plastics44. (It is limited to J3, but the current situation is that the development of new base materials has not been examined.

[Purpose of the invention]

An object of the present invention is to provide a resin polymer that maintains the heat resistance properties 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 M material consisting essentially of 2% by weight or more of N-substituted methacrylimide and 98% by weight or less of an ethylenic monomer.
A cured coating of a crosslinked curable resin H material containing at least 30% by weight of at least one monomer having three or more (meth)acryloyloxy groups in the molecule. This is a characteristic feature.

[Detailed description of the invention]

In producing the heat-resistant resin polymer with excellent abrasion resistance of the present invention, the base polymer is characterized in that it substantially contains an N-substituted methacrylimide component, and is different from conventional copolymer resins. 4 fl of a heat-resistant resin was produced which exhibited higher heat-resistant molding processability and mechanical properties and was superior in productivity than had ever been achieved before.

6- In this way, a cured film of a cross-linked curable resin material consisting of a monomer having three or more (meth)acryloyloxy groups in one molecule is provided on the surface of the heat-resistant resin M material having the characteristics (9). As a result, a resin polymer was obtained which had heat resistance and R04 abrasion resistance that were unattainable up to now, and which was well-balanced in various performances.

The heat-resistant resin base polymer of the present invention substantially contains at least a maximum percent of N-substituted methacrylimide component type 2 and an ethylenic suspension.
It is a polymer or copolymer consisting of 8 m% or less. 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 present in an amount of 2% by weight or more. In order to expect clear heat resistance 11, the content is preferably 10% by weight or more.

If the amount is less than 2%, the heat resistance of the resulting polymer may be insufficient.

The N substituent in the methacrylimide component must consist of a C1 to C20 unsubstituted or substituted alkyl group or aryl group, alone or in a mixture thereof.

From the viewpoint of improving heat resistance, it is preferable that the chain length of the substituent is relatively short. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, ter+-buble groups, phenyl groups, and substituted phenyl groups, with methyl being the most preferred.

On the other hand, the ethylenic monomer component has weather resistance, transparency and mechanical properties. It is a component that holds l.

Methyl methacrylate is preferred as the ethylenic base, but in addition to the methyl methacrylate component, small amounts of other components, preferably up to 20% by weight, include methyl acrylate, edyl methacrylate, butyl methacrylate, and methacrylic acid. Siku] cohexyl.

It may contain at least one component selected from methacrylic acid pencil, methacrylic acid, acrylic acid, styrene, α-methylstyrene, and the like.

In addition to these copolymerized components, it also contains the following components /υ
That's fine.

Examples include vinylbenzene, triallyl cyanurate-1-, h-lylyl isocyanurate, and ethylene glycol.

One or more polyfunctional reactive monomers such as dimethacrylate, 1-lyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, etc.
It may also consist of.

In order to produce a heat-resistant resin base material, the above-mentioned polymer mainly composed of polymethyl methacrylate or a single methyl methacrylate, an imidizing agent such as a primary aliphatic amine or an aromatic amine, and a primary amine by heating reaction. The desired N-substituted methacrylimide polymer can be obtained by thermal condensation with a 1,3-disubstituted urea or the like.

The heat treatment temperature for producing the N-substituted methacrylimide component of the present invention is 100°C or higher, particularly 130 to 450°C, preferably 150 to 300'C. It is preferable to carry out the heat treatment in an autoclave under an inert gas atmosphere such as argon. Furthermore, in order to prevent thermal deterioration of the polymer during this heating reaction, it is also possible to add a thermal deterioration inhibitor such as antioxidant-9=.

The antioxidants mentioned here include phospha-(+- type antioxidant Hinder 1), phenol type antioxidants, sulfur type antioxidants, and amine type antioxidants.

Small Sulfur 1-based antioxidants are represented by phosphoric acid esters, and Phosphorus M1 ~ Recresil,! Examples include TI talesylphenyl phosphate, 1-liobutyl phosphite, 1-rib-1-xyethyl phosphite, and the like.

Examples of the hindered phenol antioxidant 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, 1-dienediamine, and hydroquinoline derivatives.

Preparation of a 16-polymer mainly composed of polymethyl methacrylate or methyl methacrylate, which is a raw material for preparing 1q of the N-substituted methacrylimide component described above. However, from the viewpoint of productivity, radical polymerization is preferred.

The polymerization catalyst used to obtain the above polymer is, for example, azobisisobutyroni-1-lyl, 2,2'-azobis-
Select from azobis-based catalysts such as (2,4-dimedylvalero nitrile), diacyl peroxide-based catalysts such as lauroyl peroxide, benzoyl peroxide bis(3,5,5-1 herimedylhexanoyl) peroxide, and Bell Carbone 1-based catalysts. I can do it.

A cured film of cross-linked curable resin is provided on the surface of the heat-resistant resin polymer (to produce a resin polymer with excellent abrasion resistance).

Various types of cross-linked curable resins can be used that have groups in their molecules that can be cross-linked and hardened. 3 or more <meta> in one molecule including sexually unsaturated groups
A cross-linked curable resin material containing 30 fiffi% or more of at least one monomer having an acryloyloxy group is preferred.

Compounds having 3 or more acryloyloxy and/or methacryloyloxy groups in one molecule include 1 to 3 acryloyloxy and/or methacryloyloxy groups.
rimedylolpropane 1 to acrylate or trimethacryle-1, 1 helimethylol ethane 1 to lyacrylate or 1 to trimethacrylate-1, pentaglycerol 1 to heliacrylate-1 or 1 to trimethacrylate-1, pentaerythritol triacrylate-1 1-or 1-remethacrylate, pentaerythri-1-1-rutetraacrylate, or tetramethacrylate-h,
Glycerin 1-reacrylate or trimethacrylate-1-, dipentaerythri-1-1-triacrylate-1-
or 1 helimethacrylate, dipentaerythri 1 helitetraacrylate, or 1 helimethacrylate 1~. Dipentaerythritol pentaacrylate or pentamethacrylate, dipentaerythritol 1 hexaacrylate 1 or hexamethacrylate 1
~Tripentaerythritol Te1~Laacryle-1-or Te1~Lamethacrylate, Tripentaerythritol Pentaacrylate-1~or Pentamethacrylate-
1-11 ~ Repenta lythritol hex 1 no acrylate or hexamethacrylate 1 ~. I ~ Repentaton lythritol to butaacrylate-1 or to heptamethacrylate-1 to polyacrylate-1 or polymethacrylate: malonic acid/trimethylol Tan/acrylic acid or methacrylic acid, malonic acid/1
- Limethylolpropane 7/acrylic acid or methacrylic acid, malonic acid/glycerin/acrylic acid or methacrylic resistant, Maron IS! ,,,/Pental ■ Lithryl 1--/Acrylic acid or methacrylic acid, succinic acid/Trimethylolethane/Acrylic acid or methacrylic acid, succinic acid/1-
Limethylolpropane/acrylic acid or methacrylic acid.

]Huccinic acid, /glycerin/acrylic acid or methacrylic acid, ]Huccinic acid/pentaerythritol/acrylic acid or methacrylic acid, adipic acid/1-helimethyl [1-luethane,
/ acrylic acid or methacrylic acid, adipic acid / l-umebrolpropane / acrylic acid or methacrylic acid, adipic acid / pentaerythritol / acrylic acid or methacrylic acid, adipic acid / glycerin / acrylic or methacrylic acid, Glutaric acid/1~
Limethylolethane/acrylic acid or methacrylic acid, glutaric acid/1~limethylolpropane/acrylic acid or methacrylic acid, glutaric acid/phosphorous acid/acrylic acid or methacrylic acid, glutaric acid/pentaerythritol/
Acrylic acid or methacrylic acid, sebacic acid / 1 to rimedyloethane / acrylic acid or methacrylic acid, hibacic acid / 1 helimethylolpropane / acrylic acid or methacrylic acid, sebacic acid / glycerin / acrylic acid or methacrylic acid, sebacic acid 7 /pentaerythritol/acrylic acid or methacrylic acid, fumaric acid/trimederol ethane/acrylic acid or methacrylic acid, fumaric acid/trimethylolpropane/acrylic acid or methacrylic acid,
fumaric acid/glycerin/acrylic acid or methacrylic acid,
Fumaric acid/pentaerythritol 1--1/acrylic acid or methacrylic acid, itaconic acid/trimedyloethane/acrylic acid or methacrylic acid, itanoic acid/trimethylate 14
= Roll propane/acrylic acid or methacrylic acid.

Saturated or unsaturated by a combination of compounds such as itaconic acid/pentaerythritol/acrylic acid or methacrylic acid, maleic anhydride/1 to rimedyloethane/acrylic acid or methacrylic acid, maleic anhydride/glycerin/acrylic acid or methacrylic acid Poly 1 ster polyacrylate or polymethacrylate; 1 helimethylolpropane toluylene diisocyanate 1-. Or to polyisocyanate 1 represented by the following general formula.

hard CO (in the formula, R is hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate-1
~, xylylene diisocyanate-1~, 4,4'-methylenebis(cyclohexylisocyanate-1~), isophorone diisocyanate or 1-helimethylhexamethylene diisocyanate. ) and acrylic monomers containing active hydrogen, such as 2-hydroxyethyl acrylate or methacrylate,
2-Hydroxypropyl acrylate or methacrylate, 2-hydroxy-3-methoxypropyl acrylate or methacrylate, N-methylolacrylamide or methacrylamide, N-hydroxyacrylamide or (methacrylamide, etc.) - Urethane acrylate-1 obtained by reacting 3 moles or more per molecule in a conventional manner; Other 1 - 1 of lith + 2-hydroxyethyl + isocyanuric acid - Reacrylay 1 - or 1 - Remethacrylate-1 - etc. can be mentioned.

In addition, as a monomer having three or more (meth)acryloyloxy groups in one molecule, the following general formula % formula % ( (2 (where n is a positive integer of 1 to 11, and X is at least 3 or more are CH2=Cl-1-〇〇〇- group or Ct1
2=C(CI-1a)Coo- group, the rest is -0
1-1 group. ) It is particularly preferable to use a compound represented by the following.

Specific examples of the monomer represented by the general formula (n) include dipentaerythritoltri(meth)acryle-+-, dipentaerythritol-1-ltetra(meth)acryle-1-,
dipentaerythritol penta(meth)acrylate,
Dipentaerythri 1~-ruhexa(meth)acrylate-1
-11~riventaerythritol tri(meth)acrylate, tripentaerythritolte]・(meth)acrylate, 1~ripentaerythritol penta(meth)
Acryle 17- -1 ~, 1 ~ Repentaerythri 1 ~ -ruheki + J (meth)acrylate, etc. can be mentioned, but these monomers can be used in normal air even if not under an inert gas atmosphere such as nitrogen or argon. It is particularly preferred because it can be easily cured by irradiation with active energy rays and 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 above-mentioned 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 two or less (meth)acryloyloxy groups in one molecule. monomers having groups, such as 2,2-bis<4-acryloxydie-1hexyphenyl>propane, 2,2-bis=18=(4-methacryloxyil-xyphenyl)propane, diethylene glycol di(meth)acrylate -1-, l
-Lyethylene glyc]-di(meth)acrylate, del
-Laethylene glycol dimethacrylate, 2-hydroxyethyl (meth)acrylate-1.

Te1-Rahydrofurfuryl (meth)acrylate-1-.

Examples include ethylcarpitol (meth)acrylate. One or more of these monomers are selected and used in an amount of 70% by weight or less in the crosslinked curable resin material.

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 the active energy ray, 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-1~ represented by the general formula (IT) has the following general formula (■): (In the formula, at least three R's are Ct-12=CI-1-COO- groups, and the rest are −
1-1, a hydroxyl group, an amino group, an alkylene group, or a substituted alkylene group; nl, n2. n3. n4
°ml, ml, m3, and m4 are either 0.1 or 2, and x is a positive integer from 1 to 1o. ), for example, malonic acid/1 to rimedyloethane/acrylic acid, malon 1/1 to rimedylolpropane/acrylic acid, succinic acid/trimedylloltan/acrylic acid, succinic M/trimethylolpropane/ Esterification reaction products synthesized from combinations of compounds such as acrylic acid, adipic acid/1-listyrolethane/acrylic acid, or adipic M/l-limethylolpropane/acrylic acid, and compound (■)/compound ( I[I)=5
When used together in a ratio of 115 to 115, the weather resistance of the resulting molded article, especially accelerated 111 dew, roughness due to natural exposure,
It is particularly preferable because changes in appearance such as cracks, film peeling, and poor adhesion are prevented.

〔Effect of the invention〕

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

Fields where such heat-resistant resin polymers with excellent abrasion resistance are required include, for example, CRT filters, television filters, taximeters, digital display boards, and other display-related lighting optical-related applications, and fluorescent display tubes. Filter In addition to applications such as liquid crystal filters,
It is of extremely high commercial significance and value as it can be used in automobile headlights, power bars, etc., and can therefore respond to advances in car electronics.

The features and effects of the present invention as described above will be further explained with reference to Examples.

a) Measurement and evaluation in Examples were carried out in the following manner.

(1) Abrasion resistance a) Surface hardness Pencil hardness according to JIS K56'51-1966 b) Scratch test Scratch test with #000 steel wool I ~ ○ - Even if lightly rubbed, the surface will hardly be scratched.

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

×- If you rub it lightly, the surface will be seriously scratched 22- arrive.

(Same level as the base resin) (2) Cross-cut-cellotape peel test for adhesive cross-linked cured film 0 In other words, mark 11 film cutting lines vertically and horizontally that reach the base material at 1 mm intervals on the film, and set the scale of 1ml 112 to 100. After making each piece, apply cellophane tape on top of it and quickly peel it off.

Repeat this Hirotape operation three times at the same location (.

No peeling of cross-linked cured film even after repeating 0-3 times.

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

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

(3) Surface smoothness measurement 〇-The smoothness of the coating is very good and can be said to be a mirror surface.

8 - The surface of the coating has good smoothness, but there are slight disturbances and it cannot be said to be a mirror surface.

There is disturbance in the x-direction and the smoothness is poor.

Example 1 1 part of tert dodecyl mercaptan and 0.4 parts by weight of lauroyl peroxide were added to and dissolved in a 100-piece suspension of methyl meccrylate, and then two polyvinyl chloride gaskets were placed facing each other at an interval of 3 mm through gaskets 1 to 1. A thermal lightning pair was applied to a cell formed from a tempered glass plate, and the monomer solution was injected into the cell, immersed in 80°C warm water, and 30 minutes after the internal temperature reached its peak. 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 cell was removed, and the resin plate, which had been cracked once and had a thickness of 6 ml, was pulverized in a clean box. Obtained polymer M
I (230℃ load 3.8Ko) is 13.0, refractive index ND 1.4920, specific gravity 1.190, heat distortion temperature 10
It was 5℃. 1 for this polymer 100 heavy hanging part.
22 parts by weight of 3-dimethylurea, 4.5 parts by weight of water, 2.6 parts by weight of Antige Bl-IT (manufactured by Kawaguchi Chemical Co., Ltd.)
Butyl-P-cresol) 0.01 part by weight was charged into a 3a volume oak crepe and nitrogen purging was repeated until 23 minutes.
The transparent resin body PolyN was heated and reacted in a 0℃ oil bath for 4 hours.
- A methyl methacrylimide polymer was obtained.

From the infrared absorption spectrum, it is 1770.1663.750
Absorption peculiar to N-methylmethacrylimide was observed at c+++-1.

MI of the obtained polymer (230℃ load 3.8Ko
) was 3.5, the refractive index was 1.536, the specific gravity was 1.210, and the heat distortion temperature was 175°C.

Next, this polymer was extruded using a 25φ vented extruder (Die temperature: 230°C, adapter temperature: 230°C, screw barrel temperature: 200-230°C, full-flight screw L/D = 24, manufactured by Jitsugyo Kyoku). It was made into mock pellets. Using this polymer formed into pellets 1, a heat-resistant flat molded plate (80 x 80 x 2 mm) was obtained using a 1-ounce vertical screw. The surface hardness was 21-1 in terms of pencil hardness. As a result of the abrasion test with STI 25-1 wool, the surface was seriously scratched when it was lightly applied.

Dipentaerythritol pentaacrylate - 1 to 30 parts,
dipentaerythritol hexaacryle]~30 parts, dipentaerythritol tetraacrylate-1~20
20 parts of 2-hydroxyethyl acrylate and 4 parts of benzoin ethyl ether were mixed with 200 parts of isopropanol-toluene (6/4) mixed solvent.
The resin was coated uniformly on the molded resin plate by dip coating using the above-mentioned resin molded plate, and then cured by irradiation with ultraviolet rays emitted from a high-pressure mercury lamp.

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

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.

26- Example 2 The polymer consisting of methyl methacrylate of Example 1 was used as it was, and for every 100 polymer parts, 1.3 dimethylurea 11 parts, water 2.25 parts, anti- 981
A N-I methyl methacrylimide methyl methacrylate copolymer was obtained by heating reaction in O 1 to crepe using 0.01 part by weight of 1 F. The imidization rate was 45% from the infrared absorption spectrum. The MI of the obtained polymer was 4.3
, refractive index 1.510, specific gravity 1.21, heat distortion temperature 149
It was ℃. A resin flat plate was obtained in the same manner as in Example 1. The surface hardness was 1-1 on a pencil hardness scale. As a result of la (1 m dest) with steel wool, the surface was severely scratched when lightly rubbed.

The cross-linked curable resin material of Example 1 was cured by irradiation with ultraviolet rays emitted from a high-pressure mercury furnace.

The surface obtained in this way has a cross-linked cured film of approximately 3 μm.
The heat-resistant resin plate was hardly scratched even when an abrasion resistance test was performed using #OOO steel wool, and the pencil hardness was 711.

In addition, the cross-linked cured coating is extremely hard and has excellent adhesion to the substrate, and the tape peel test was extremely good, indicating that the coating was flat. N bamboo had a very good mirror finish.

Example 3 The polymer obtained from methyl methacrylate in Example 1 was used as it was, and for 100 parts by weight of the small polymer, 1 part by weight of Antige Bl-ITO, 1 part by weight, dry medylamine] 5@■
71 people in a crepe to O1 and N- due to heating reaction.
A methyl methacrylimide polymer was obtained.

After creating a flat molded plate by the method according to Example 1, Dipentaerythri 1 Hel Pentaacrylate 1-10 parts Dipentaerythri 1--Rheki 1j Acrylay 1.10
Part Tetrahuman Day Furfuryl Acrylic - 1 to 8 Part Amber M
Ester obtained by reacting 1 mole/2 moles of trimethylolethane/4 moles of acrylic acid 7 parts isopropyl alcohol, 35 parts 1-lune 3 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 thus obtained was excellent in abrasion resistance, adhesion, and smoothness.

Example 4 A copolymer was obtained according to Example 1 using a monomer composition consisting of 80 parts of methyl methacrylate and 20 parts of methacrylic acid.

40 parts of a 40% methylamine aqueous solution was charged to 100 parts by weight of the obtained polymer in an O-1 crepe, and an imidization reaction was carried out by heating, to obtain an N-methylmethacrylimide polymer. J to the method according to Example 1:
After creating a flat molded plate, it was immersed in the crosslinked curable resin material solution used in Example 3.
! After applying it evenly with a cloth, it is cured by irradiating it with ultraviolet light emitted from a high-pressure mercury lamp.

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

Agent Asamura Hako 30-

Claims (2)

[Claims] (1) Structural formula: (wherein R represents an alkyl group or an aryl group having 1 to 20 carbon atoms)
At least 30% by weight of at least one single substance having 3 or more (meth)acryloyloxy groups in one molecule is added to the surface of a resin molded product consisting of the above and 98% by weight or less of ethylenic monomer units. A heat-resistant resin molded product with a hardened coating of a cross-linked curable resin material containing (-). (2) Structural formula: (wherein R represents an alkyl group or aryl group having 1 to 20 carbon atoms) N-substituted methacrylimide 4f? i building unit 2
At least 30% by weight of at least one monomer having 3 or more (meth)acryloyloxy groups in one molecule is applied to the surface of a resin molded product consisting of 5% or more and 98% by weight or less of ethylenic monomer units. A heat-resistant product with excellent abrasion resistance characterized by applying a cross-linked hardening abrasive material having a hardening content of less than 10% and then irradiating active energy rays to form a cross-linked hardened film on the surface of the resin molded product. A manufacturing method for synthetic resin molded products.