JPH0625272B2 - Synthetic resin molding manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a surface hardness obtained by coating a surface of a molded article made of a polymer of a compound having 3 or more allyl carbonate groups in one molecule with a curable substance, The present invention relates to a synthetic resin molded product having excellent scratch resistance and solvent resistance.

[Conventional technology]

Generally, synthetic resin molded products are used in various fields by taking advantage of their light weight, local workability, impact resistance, etc., but on the other hand, their surface hardness is low, so they are easily worn and damaged, and they also come into contact with solvents. Swelling and dissolution tend to occur, which is a major obstacle to practical use. That is, as such synthetic resin, for example, polyunsaturated esters such as polymethylmethacrylate, polystyrenes, polyvinyl chloride, epoxy resins, polyamides, polymers such as polycarbonates, or monomers forming these polymers or Examples thereof include copolymers of the monomer and other monomers, and molded products thereof are mainly targeted for optical materials such as synthetic resin lenses, prisms and flat sheets, and generally have high transparency but low surface hardness, Poor scratch resistance and abrasion resistance.

Therefore, conventionally, for the purpose of improving these drawbacks, a method of imparting a crosslinked structure to a synthetic resin and forming a hard coating film on the surface of a synthetic resin molded article as a secondary processing have been performed.

[Problems to be solved by the invention]

However, in the conventional molded article of synthetic resin having a hard film formed thereon, the cloth (property) of the synthetic resin appears on the surface even though the base material of the synthetic resin has a crosslinked structure. In particular, the improvement of scratch resistance is not sufficiently achieved, and it is considerably inferior to that of glass. For example, if the scratch resistance of the glass is A rank and the scratch resistance of the polymer of diethylene glycol bisallyl carbonate is E rank, the scratch resistance of the diethylene glycol bisallyl carbonate polymer is C rank only when a hard coating is applied to the polymer. Does not improve.

This cannot be said to have sufficiently solved the problem of impairing transparency due to abrasion and scratches, especially in optical materials made of synthetic resin.

[Means for solving problems]

In view of the above, the present inventors have conducted diligent research on a curable substance and a synthetic resin substrate for the purpose of improving the surface characteristics of a synthetic resin molded product, and as a result, coat the surface of the specified synthetic resin substrate with the curable substance. In this case, the synergistic effect of the two results in the finding that the surface hardness is improved and the intended purpose is achieved, and further, means for further improving the integrity of the base material and the coating and the uniformity of the coating are provided. It was found that the present invention has been completed. That is, the present invention is characterized in that the surface of a substrate made of a polymer of a carbonate compound having three or more allyl carbonate groups in one molecule is subjected to alkali treatment, and then a curable substance is coated and cured. It is a method for producing a transparent synthetic resin molded product in which a cured raw material is coated.

According to the present invention, a synthetic resin comprising a polymer of an allyl carbonate compound having three or more allyl carbonate groups in the above-specified molecule having good scratch resistance (hereinafter, also simply referred to as allyl carbonate polymer) By coating the surface of the base material with a curable substance, it is possible to obtain a transparent synthetic resin molded product having extremely excellent surface hardness and scratch resistance. That is, the transparent synthetic resin molded article of the present invention uses a synthetic resin of a carbonate polymer having excellent scratch resistance as a base material, but the scratch resistance of the synthetic resin base material and the scratch resistance of the curable coating are Due to the synergistic effect of, it has extremely higher scratch resistance than expected.

In the present invention, the carbonate compound, which is a raw material of the synthetic resin base material, contains three or more carbonate compounds in one molecule. There is no particular limitation as long as it has an allyl carbonate group represented by. Specifically, the following compounds may be mentioned.

(1) General formula An allyl carbonate compound represented by.

Here, the alkyl group and the alkoxy group have no limitation on the number of carbon atoms, but the number of carbon atoms is preferably in the range of 1 to 10 in consideration of the surface hardness of the resin obtained by polymerization. Examples of the aryl group include phenyl group, tolyl group, xylyl group, naphthyl group, anthryl group, phenanthryl group, benzyl group and the like. As a substituent of these alkyl groups and aryl groups, a halogen atom,
A hydroxyl group, an alkoxy group, an epoxy group, etc. can be mentioned. Further, in the above general formula [I], m may be an integer of 0 or more, but from the viewpoint of the hardness of the obtained resin, m is 0.
It is preferably an integer of -30. Further, l may be an integer of 1 or more, but is preferably an integer of 1 to 20.

(2) General formula An allyl carbonate compound represented by.

In the above general formula [II], as the halogen atom represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , fluorine, chlorine, bromine and iodine atoms are adopted. Further, k may be an integer of 1 or more, but in order to make the viscosity of the allyl carbonate compound represented by the general formula [II] an appropriate value and facilitate handling, k is an integer of 1 to 3. Preferably there is.

(3) General formula [III] An allyl carbonate compound represented by.

(4) An allyl carbonate compound in which three or more hydroxyl groups of carbohydrate are substituted with allyl carbonate groups.

Examples of the above-mentioned carbohydrates include glycerin, glucose, fructose, mannose, galactose, glucopyranose, xylopyranose, arabinose, fructopyranose, xylulose, xylulose 5-phosphate, sorbitol, maltose, cellobiose, isomaltose, lactose, sucrose, amylose. Etc.

The allyl carbonate compound used in the present invention is preferably an allyl carbonate compound represented by the above general formulas [I] and [II], from the viewpoints of transparency of the polymer, scratch resistance, and the like. The allyl carbonate compound represented by [I] is most preferable. Specific examples of the allyl carbonate compound preferably used in the present invention include, for example, Etc. can be mentioned.

In addition, in the present invention, other copolymerizable compounds may be added together with the above-mentioned allyl carbonate compound to the extent that the scratch resistance of the synthetic resin substrate is not impaired. Such copolymerizable compounds include, for example, ethylene glycol bisallyl carbonate (EG-BAC), diethylene glycol bisallyl carbonate (DEG-BAC), in order to improve the impact resistance of synthetic resin substrates.
Polyethylene glycol molecular weight is 200, 300, 400, 600
Polyethylene glycol bisallyl carbonate (PEG-200-BAC, PEG-300-BAC, PEG-400-BAC, PEG-600-B
AC), and to improve the refractive index of synthetic resin base materials such as styrene, divinylbenzene, chloromethylstyrene, diallyl terephthalate, benzyl methacrylate, and bisphenol A dimethacrylate.
1.5 or more copolymerizable compounds are used.

The synthetic resin base material of the present invention is a polymer of a compound as described above or a copolymer of the compound with another compound, which is a known radical polymerization compound in the presence of a radical polymerization initiator or under irradiation of ultraviolet rays or radiation. It can be obtained by using the method without particular limitation.

Further, in the polymerization, a releasing agent, an ultraviolet absorber, an antioxidant, a coloring preventing agent, an antistatic agent, various stabilizers such as a fluorescent dye, and additives can be selected and used as necessary.

The curable substance used in the present invention includes heat, catalyst, curing agent, light,
A so-called crosslinkable substance which reacts with radiation or the like and particularly forms a three-dimensional network structure to form a hard coating can be used without limitation. For example, a melamine-based curable composition composed of melamines and other reactive substances such as formaldehyde, an acrylic-based curable composition composed of acrylic acid esters and acrylic acid amides, epoxys and bisphenol A, etc. An epoxy-based curable composition composed of a reactive substance, a silicon-based curable composition composed of an organosilicon such as methyltrimethoxysilane, or a known curable composition obtained by combining these is preferably used.

In addition, specific examples of a coating composition of a curable substance are (1) a disilane compound represented by the general formula (RO) ₃ Si-A-Si (OR) ₃ (where R is a methyl group, The same or different alkyl group selected from ethyl group, propyl group and butyl group; A is a divalent functional group in which at least 4 atoms are linearly bonded) Composition (2) general formula A disilane compound containing an epoxy group represented by (wherein A is a divalent atomic group containing an epoxy group and having a main chain of at least 6 atoms in a straight chain, R ¹ and R ² are the same or different) Of Alkyl group or Alkoxyalkyl group, R ³ and R ⁴ are the same or different alkyl groups, and 1 and m are 0 or 1). A disilane compound represented by (wherein k is 2 or 3, R ¹ and R ² are the same or different alkyl groups, R ³
And R ⁴ are the same or different alkyl groups, and 1 and m are 0.
Or 1) is a constituent.

And so on.

One of the features of the method for producing a synthetic resin molded article of the present invention is that the surface of a predetermined synthetic resin substrate is previously treated with an alkali, and then a curable substance is coated and cured to form a film of the curable substance. Can be obtained with good adhesion.

The alkali treatment solution is not particularly limited, and examples thereof include amines, alkali metal hydroxides and alcoholates, and basic compounds such as ammonia, which may be used alone or as a mixture of two or more thereof. The solvent can be used without particular limitation as long as it can dissolve the above basic compound, but water is usually used from the viewpoint of solubility and workability. As the treatment method, an immersion method, a spray method, a flow method and the like can be mentioned. From the viewpoint of workability, the immersion method of immersing in an alkaline solution is preferable. The treatment time is not particularly limited and may be determined in consideration of the adhesion between the molded product and the hard coating.

As a method of coating a curable substance on a molded product made of a polymer of a compound having three or more allyl carbonate groups in one molecule of the present invention, known methods can be used without particular limitation. For example, a dipping method, a flow coating method, a brush coating method, a rotation method and the like are generally adopted. The thickness of the coating film is not particularly limited, but is generally 0.1 μ to 50 μ. Further, the curing of the curable substance may be appropriately performed according to its type.

〔The invention's effect〕

As described above, according to the present invention, a molded product of a substrate having excellent scratch resistance, which is made of a polymer of a compound having 3 or more allyl carbonate groups in one molecule, is provided with a hard coating having good scratch resistance and durability. Coated especially excellent in scratch resistance, adhesion,
It is possible to provide a synthetic resin molded product having excellent heat resistance and chemical resistance.

〔Example〕

Hereinafter, examples and comparative examples will be shown in order to specifically describe the present invention, but the present invention is not limited to these examples.

The surface properties of a synthetic resin molded product obtained by coating a surface of a molded product of a polymer of a compound having three or more allyl carbonate groups in one molecule with a curable substance were evaluated by the following methods.

(1) Scratch resistance # 0000 on the scratch resistance tester manufactured by Fukuda Machine Industry Co., Ltd.
After the steel wool was attached and the sample surface was reciprocated 10 times under a load of 1 kg, the degree of scratches on the surface was visually observed, and the state where no scratch was observed was A, and the diethylene glycol bisallyl carbonate resin fabric was very easily scratched The state is E, and B, C, D between A and E
It was divided into 5 categories and evaluated.

(2) Adhesion test 1 mm x 1 mm on the surface of the sample with a cutter knife having a sharp tip
After attaching 100 squares, attach a commercially available cellophane tape, and then observe the peeling state of the coating when peeling quickly, and check the number of squares remaining without peeling within 100 squares evaluated.

(3) Hot water resistance test After leaving in boiling water for 2 hours, the above adhesion test is performed.
It was evaluated according to the same criteria.

(4) Chemical resistance The weight increase after immersion in a chemical such as ethanol, acetone, 5% HCl, 5% NaOH for 4 days at 25 ° C. is shown as a weight percentage, and the weight increase amount is less than 0.5% by weight. 0.5-1.0
Weight% was evaluated as acceptable, and 1.0% by weight or more was evaluated as unacceptable.

The curing method using the curable substance or the curable composition used in Examples and Comparative Examples is shown below.

(I) 20 parts by weight of methyltrimethoxysilane, 10 parts by weight of γ-glycidoxypropyltrimethoxysilane, 10 parts by weight of tetraethoxysilane, 20 parts by weight of 0.05N hydrochloric acid necessary for hydrolysis, 40 parts by weight of isopropyl alcohol, and curing Sodium acetate / acetic acid (1/10) as catalyst
A predetermined molded article is dipped in a curable substance consisting of 1 part by weight of the mixture of 3 to coat, and this is air-dried at room temperature sufficiently.
It was cured by heating at 0 ° C. for 1 hour.

(II) 20 parts by weight of bis (γ-triethoxysilylpropyl) carbonate, 10 parts by weight of γ-glycidoxypropyltrimethoxysilane, 30 parts by weight of colloidal silica (Methanol sol manufactured by Nissan Chemical Co., Ltd.), 30 parts by weight of methicello, 0.05
A predetermined molding is dipped in a curable substance consisting of 10 parts by weight of normal hydrochloric acid and 0.25 parts by weight of ammonium perchlorate as a curing catalyst to coat the product, and the resulting product is sufficiently air-dried at room temperature.
It was cured by heating at 0 ° C. for 1 hour.

(III) 50 parts by weight of trimethylolpropane triacrylate, 50 parts by weight of triethylene glycol diacrylate, and 1 part by weight of benzophenone are dissolved in 50 parts by weight of isopropyl alcohol, and a predetermined molded article is dipped and coated with the curable composition. After thoroughly air-drying with nitrogen at room temperature, it was cured under UV irradiation.

(IV) Hexamethoxymethylmelamine (25 parts by weight) and 2-hydroxyethyl methacrylate (25 parts by weight) were mixed and dissolved in 50 parts by weight of methyl cellosolve, and 0.2 parts by weight of ammonium thiocyanate was added to the mixture to prepare a predetermined curable substance. The molded product was dipped and coated, sufficiently air-dried at room temperature, and then heat-cured at 130 ° C. for 1 hour.

Example 1. As a molded article made of a polymer of a compound having three or more allyl carbonate groups in one molecule, trimethylolpropane triallyl carbonate is added to diisopropyl peroxydicarbonate (hereinafter, as a radical polymerization initiator).
(Abbreviated as IPP) was added in an amount of 2.2 parts by weight, and a plate-shaped body excellent in scratch resistance, which was produced by ordinary cast polymerization, was used. The scratch resistance of the plate was C. First, as a pretreatment, the plate-like body was washed with acetone, air-dried sufficiently to be clarified, then immersed in an alkaline solution under the conditions shown in Table 1, and then washed with water and dried. The above plate-like body was subjected to the treatment method (I) with a curable substance to form a hard coating. Table 1 also shows the evaluation results of the surface of the coated synthetic resin molded product.

Example 2. A film was formed in the same manner as in Example 1 except that NaOH was used as the basic compound. Table 2 shows the evaluation results of the surface of the coated synthetic resin molded product.

Example 3. After washing the synthetic resin plate made of the polymer of trimethylolpropane triallyl carbonate having excellent scratch resistance of Example 1 with acetone and thoroughly air-drying it to a clear state,
As an alkaline solution treatment, it was immersed in a 10% NaOH aqueous solution for 10 minutes, then washed with water and dried.

A method for treating the above plate-like body with a curable substance (II), (II
It was subjected to I) and (IV) to form a hard coating. Table 3 shows the evaluation results of the surface of the coated synthetic resin molded product.

Example 4. As a molded article made of a polymer of a compound having 3 or more allyl carbonate groups in one molecule, trimethylolpropane-triallyl carbonate and various polyalkylene glycol bisallyl carbonates shown in Table 4, and various kinds of polyalkylene glycol bisallyl carbonate shown in Table 5 A plate-like body produced by cast polymerization by adding 2.2 parts by weight of IPP to each mixed solution of copolymerizable compounds having a refractive index of 1.5 or more was thoroughly washed with acetone, air-dried and clarified. After that, it was dipped in a 10% NaOH aqueous solution for 10 minutes, washed with water and dried.

The plate-shaped body was dip-coated by the pretreatment method (II) with a curable substance to form a cured coating.

Each of the synthetic resin molded products had a surface scratch resistance of B, initial adhesion and hot water resistance of 100, and good chemical resistance.

Example 5. As a synthetic resin substrate, a plate-like body prepared by ordinary cast polymerization by adding 2.2 parts by weight of IPP to each compound having 3 or more allyl carbonate groups in one molecule shown in Table 6 was used.

First, as a pretreatment, it was thoroughly washed with acetone, sufficiently air-dried to be clarified, then immersed in a 10% NaOH aqueous solution for 10 minutes, then washed with water and dried.

The plate-shaped body was dip-coated by the pretreatment method (II) with a curable substance to form a cured coating.

Claims (1)

[Claims] 1. A surface of a substrate comprising a polymer of a carbonate compound having three or more allyl carbonate groups in one molecule, which is treated with an alkali and then coated with a curable substance to be cured. Method for producing synthetic resin molded product coated with curable substance