JPH0857864A - Acid phosphonic acid derivative-based internal releasant and molding method and molded matter used thereof - Google Patents

Abstract

PURPOSE: To obtain malodor-free internal releasant excellent in transparency and releasability by a method wherein the releasant contains acid phosphonic acid derivative. CONSTITUTION: Acid phosphonic acid derivative is compound represented by the formula, in which R1 and R2 may well be equal to each other or different from each other and are hydrogen atom or 1-20C alkyl residue, 1-20C aryl residue, 1-20C alkoxyalkyl residue, 1-20C alkylene residue, 1-20C alloalkyl residue, 1-20C alloaryl residue or 1-20C alloalkoxyalkyl residue, and included in internal releasant. Resin molded matter, concretely plastic lens made thereof is obtained through molding, in which the releasant is employed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an internal mold release agent, a resin molding method using the same, and a resin molded product obtained by the molding method. It is characterized by improving the releasability and obtaining a transparent resin molded product with less turbidity. Therefore, plastic lenses, prisms, which require surface precision and transparency,
The present invention is useful in molding optical products such as optical disk substrates and optical fibers, but is also useful in molding other resins because of its excellent mold releasability.

[0002]

2. Description of the Related Art There are various methods for molding a resin, such as mold polymerization and injection molding. In any case, a so-called mold release agent is used for improving the mold releasability between a molded product and a mold. In particular, urethane resin, epoxy resin and the like have a strong adhesive force and it is essential to use a release agent.

Release agents are roughly classified into external release agents and internal release agents. The external mold release agent has to be applied to the inner surface of the mold each time it is molded, so the productivity of the molded product is poor, and the external mold release agent migrates to the surface of the molded product, causing unevenness on the surface of the molded product. However, there are problems such as poor painting and dyeing, and turbidity of the transparent resin molded product. On the other hand, the internal release agent is a release agent added in advance to the resin raw material monomer, and it is not necessary to apply the release agent to the mold every time, which is advantageous for improving productivity.

Conventionally known internal release agents include fluorine-based nonionic surfactants for molding urethane resins,
Silicon nonionic surfactant, alkyl quaternary ammonium salt, acidic phosphate ester, liquid paraffin, wax, higher fatty acid and its metal salt, higher fatty acid ester, higher fatty alcohol, bisamides, polysiloxanes, aliphatic Amine ethylene oxide adduct (JP-A-1-295201), and a phosphate ester having a polyether substituent (JP-A-3-28764)
Etc.

Further, in the reaction injection molding method of urethane resin, zinc stearate is generally used. However, since zinc stearate has poor solubility in raw materials, patents for various compatibilizers have been filed ( JP-A-3-273030, JP-B-3-2758
No. 6).

In the molding of epoxy resin, a method of using zinc stearate as an internal mold release agent (Japanese Patent Laid-Open No. 1-1999)
No. 213602), a fluorine-based nonionic surfactant,
There is a method (JP-A-3-81320) in which a silicon-based nonionic surfactant, an alkyl quaternary ammonium salt, an acidic phosphoric acid ester or the like is used as an internal mold release agent. Method in which a mold agent is used in combination (JP-A-63-144302, JP-A-63-144303)
No. publication) is known.

In addition, in the molding of polyolefin resin, an aliphatic alcohol, an aliphatic ester, a phthalic acid ester, a triglyceride, a fluorochemical surfactant, a higher fatty acid metal salt, etc. are used as an internal mold releasing agent (Japanese Patent Laid-Open No. HEI 2). No. 84409, Japanese Patent Application Laid-Open No. 2-44301), higher fatty acid ester, wax, liquid paraffin, silicone oil, alkyl glyceryl ether and the like are used as internal mold release agents in the molding of polycarbonate resin (Japanese Patent Application Laid-Open No. No. 315460, Japanese Patent Laid-Open No.
No. 315459), a molding method in which higher alcohols, higher fatty acid esters, higher fatty acids and the like are used as an internal mold release agent is also generally used for acrylic resins (JP-A-2-105844).

These known internal mold release agents are more effective than the external mold release agents in improving productivity, but they do not have sufficient mold release performance and resin remains on the mold surface during mold release,
In the case of a glass mold, peeling of glass may occur. Further, there is a case in which excessive stress is applied due to resistance at the time of mold release, and warping or distortion occurs in the molded product. Furthermore, there is a problem that the molded product tends to become turbid at the amount used to sufficiently satisfy the releasability. These drawbacks are fatal particularly in the molding of optical products such as plastic lenses and optical discs, in which surface accuracy and transparency are important, and significantly reduce the commercial value.

As a method for improving these drawbacks, the present inventors have proposed an acidic thiophosphate ester internal release agent (JP-A-5-306320). This acidic thiophosphoric acid-based internal release agent is a urethane resin, epoxy resin, polyolefin resin, polyene-polythiol resin, unsaturated polyester resin, phenol resin, furan resin, xylene resin, formaldehyde resin, ketone resin, urea resin, melamine resin. , Transparent resin such as aniline resin, sulfonamide resin, alkyd resin, polycarbonate resin, thermoplastic polyester resin, polyether resin, polyamide resin, polyimide resin, polyvinylketone resin, polyvinyl ether resin or composite resin thereof, resin It is an internal mold release agent that gives excellent mold releasability without impairing the transparency.

However, since the acidic thiophosphoric acid internal release agent itself is a compound having a strong unpleasant odor, for example, in the work of adding it to the raw material monomer in advance, it always involves unpleasant odor. There is a problem that some people may feel uncomfortable due to the unpleasant odor. In order to avoid this problem, work may be carried out in a draft or the like, but it is uneconomical because the operability is reduced and the equipment cost of the draft equipment and the associated detoxification equipment are required. Therefore, the development of an internal mold release agent with no unpleasant odor by improving the odor of the acidic thiophosphoric acid ester internal mold release agent and giving the same transparency and mold release property as the acidic thiophosphate ester internal mold release agent. Was strongly desired.

[0011]

SUMMARY OF THE INVENTION The first object of the present invention is to provide an internal mold release agent which gives excellent transparency and mold release property and has no unpleasant odor. The second object is to provide the internal mold release agent. The third object is to provide a resin molded product obtained by the molding method.

[0012]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have surprisingly found that an acidic phosphonate ester has no unpleasant odor and is as excellent as an acidic thiophosphate ester. The present invention has been achieved by finding that it imparts transparency and releasability.

That is, the present invention is an internal release agent containing an acidic phosphonic acid derivative. The acidic phosphonic acid derivative has the formula (1)
A compound represented by:

[Chemical 7] [In the formula (1), R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl residue having 1 to 20 carbon atoms, an aryl residue having 1 to 20 carbon atoms, or a carbon atom. Alkoxyalkyl residue having 1 to 20 carbon atoms, or alkylene residue having 1 to 20 carbon atoms, or 1 to 20 carbon atoms
Represents an araalkyl residue having 1 to 20 carbon atoms, an araaryl residue having 1 to 20 carbon atoms, or an araalkoxyalkyl residue having 1 to 20 carbon atoms. Or a compound represented by the formula (2)

Embedded image [In Formula (2), X is represented by Formula (3) (Chemical Formula 9), and in Formula (3), m represents an integer of 1 to 10 and n represents an integer of 0 to 4.

[Chemical 9] In formula (2), R ₃ and R ₄ may be the same or different and each is a hydrogen atom, an alkyl residue having 1 to 20 carbon atoms, an aryl residue having 1 to 20 carbon atoms, or a carbon number. Alkoxyalkyl residue having 1 to 20 carbon atoms, alkylene residue having 1 to 20 carbon atoms, araalkyl residue having 1 to 20 carbon atoms, araaryl residue having 1 to 20 carbon atoms, or 1 carbon atom Represents up to 20 araalkoxyalkyl residues. ] The internal mold release agent which is. A compound whose acidic phosphonic acid derivative is represented by formula (4)

[Chemical 10] [In the formula (4), R ₅ is a hydrogen atom or a carbon number of 1 to 10
Up to an alkyl residue, or an alkoxy residue having 1 to 10 carbon atoms, or an alkylene residue having 1 to 10 carbon atoms,
Or an araalkyl residue having 1 to 10 carbon atoms, an araalkoxy residue having 1 to 10 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and p is 0 to 5
Represents the integer. R ₆ is a hydrogen atom or a carbon number of 1 to 20
Up to an alkyl residue, or an aryl residue up to 1 to 20 carbon atoms, an alkoxyalkyl residue up to 1 to 20 carbon atoms, an alkylene residue up to 1 to 20 carbon atoms, or up to 1 to 20 carbon atoms Araalkyl residue of, or 1 carbon atom
Up to 20 araaryl residues or 1 to 20 carbon araalkoxyalkyl residues. Or a compound represented by the formula (5)

[Chemical 11] [In Formula (5), X is represented by Formula (6) (Chemical Formula 12), and in Formula (6), s represents an integer of 1 to 10 and t represents an integer of 0 to 4. ]

[Chemical 12] [In the formula (5), R ₇ and R ₈ may be the same or different and each is a hydrogen atom, an alkyl residue having 1 to 10 carbon atoms, or an alkoxy residue having 1 to 10 carbon atoms, or Alkylene residue having 1 to 10 carbon atoms, or 1 carbon atom
An araalkyl residue of up to 10 or an araalkoxy residue of 1 to 10 carbon atoms, a fluorine atom, a chlorine atom,
It represents a bromine atom or an iodine atom, and q and r represent an integer of 0 to 5. ] The internal mold release agent which is. A method of molding a resin using the release agent, a resin molded product obtained by the method, and a plastic lens comprising the resin molded product.

Specific examples of the acidic phosphonic acid derivative represented by the formula (1) include, for example, phosphonic acid, methyl phosphonate, ethyl phosphonate, propyl phosphonate, isopropyl phosphonate, butyl phosphonate, isobutyl phosphonate and phosphonate. Acid sec-butyl, phosphonic acid ter
t-butyl, hexyl phosphonate, octyl phosphonate, 2-ethylhexyl phosphonate, decyl phosphonate, dodecyl phosphonate, tetradecyl phosphonate, hexadecyl phosphonate, octadecyl phosphonate, eicosanyl phosphonate, phenyl phosphonate, naphthyl phosphonate, Tolyl phosphonate, methoxyphenyl phosphonate, phenoxyphenyl phosphonate, methoxyethyl phosphonate, phenoxyethyl phosphonate, allyl phosphonate, benzyl phosphonate, biphenyl phosphonate,
Benzyloxyethyl phosphonate, methylphosphonic acid,
Ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, isobutylphosphonic acid, sec-butylphosphonic acid, tert-butylphosphonic acid, hexylphosphonic acid, cyclohexylphosphonic acid, octylphosphonic acid, 2-ethylhexylphosphonic acid, Dodecylphosphonic acid, tetradecylphosphonic acid, hexadecylphosphonic acid, octadecylphosphonic acid, eicosanylphosphonic acid, phenylphosphonic acid, naphthylphosphonic acid, chlorophenylphosphonic acid, difluorophenylphosphonic acid, tolylphosphonic acid, ethylphenylphosphonic acid, tert-butylphenylphosphonic acid, cyclohexylphenylphosphonic acid, tetradecylphenylphosphonic acid, benzylphenylphosphonic acid, xylylphosphonic acid, methyl- Di tert- butylphenyl phosphonic acid, diisopropyl phenylphosphonic acid, methoxyphenyl phosphonic acid, ethoxyphenyl acid, t
ert-butoxyphenylphosphonic acid, isopropoxyphenylphosphonic acid, benzyloxyphenylphosphonic acid, dimethoxyphenylphosphonic acid, phenoxyphenylphosphonic acid, tolyloxyphenylphosphonic acid, methoxyphenoxyphenylphosphonic acid, methoxyethylphosphonic acid, ethoxyethylphosphonic acid , Propoxyethylphosphonic acid, butoxyethylphosphonic acid, methoxypropylphosphonic acid, ethoxypropylphosphonic acid, propoxypropylphosphonic acid, butoxypropylphosphonic acid, phenoxyethylphosphonic acid, biphenyloxyethylphosphonic acid, naphthoxyethylphosphonic acid, phenoxypropyl Phosphonic acid, biphenyloxypropylphosphonic acid, naphthoxypropylphosphonic acid, allylphosphonic acid, benzyl Suhon acid, biphenyl phosphonic acid,
Benzyloxyethylphosphonic acid, benzyloxypropylphosphonic acid, methyl methylphosphonate, ethyl methylphosphonate, methyl ethylphosphonate, isopropyl methylphosphonate, methyl isopropylphosphonate, butyl methylphosphonate, methyl butylphosphonate, octyl methylphosphonate, octylphosphonic acid Methyl, decyl methylphosphonate, methyl decylphosphonate, dodecyl methylphosphonate, methyl dodecylphosphonate, tridecyl methylphosphonate, methyl tridecylphosphonate, octadecyl methylphosphonate, methyl octadecylphosphonate, cyclohexyl methylphosphonate, methyl cyclohexylphosphonate, octylphosphonate Ethyl acid, octyl ethylphosphonate, isopropyl octylphosphonate, iso Ropiruhosuhon octyl, octyl phosphonic acid propyl, propyl phosphonic acid octyl,
Butyl octyl phosphonate, octyl butyl phosphonate, hexyl octyl phosphonate, hexyl phosphonate octyl, octyl phosphonate cyclohexyl, cyclohexyl phosphonate octyl, octyl phosphonate decyl, decyl phosphonate octyl, octyl phosphonate dodecyl, dodecyl phosphonate octyl, Tridecyl octylphosphonate, octyl tridecylphosphonate, octadecyl octylphosphonate, octyl octadecylphosphonate, ethyl 2-ethylhexylphosphonate, 2-ethylhexyl ethylphosphonate, isopropyl 2-ethylhexylphosphonate, isopropylphosphonate 2-
Ethylhexyl, propyl 2-ethylhexylphosphonate, 2-ethylhexyl propylphosphonate, butyl 2-ethylhexylphosphonate, 2-ethylhexyl butylphosphonate, hexyl 2-ethylhexylphosphonate, 2-ethylhexyl hexylphosphonate, cyclohexyl 2-ethylhexylphosphonate , 2-ethylhexyl cyclohexylphosphonate, decyl 2-ethylhexylphosphonate, 2-ethylhexyl decylphosphonate, dodecyl 2-ethylhexylphosphonate, 2-ethylhexyl dodecylphosphonate, tridecyl 2-ethylhexylphosphonate, 2-ethylhexyl tridecylphosphonate Octadecyl 2-ethylhexylphosphonate, 2-ethylhexyl octadecylphosphonate, ethyl ethylphosphonate, Propyl phosphonate, isopropyl isopropyl phosphonate, butyl butyl phosphonate, isobutyl phosphonate isobutyl, sec-butyl phosphonate sec-butyl, tert-butyl phosphonate tert-butyl, hexyl phosphonate hexyl, cyclohexyl phosphonate cyclohexyl, octyl phosphonate Octyl, 2-ethylhexylphosphonate 2-ethylhexyl, decylphosphonate decyl, dodecylphosphonate dodecyl, tridecylphosphonate tridecyl, tetradecylphosphonate tetradecyl, hexadecylphosphonate hexadecyl, octadecylphosphonate octadecyl, eicosanylphosphonate eicosanyl. , Methyl phenylphosphonate, phenyl methylphosphonate,
Ethyl phenylphosphonate, phenyl ethylphosphonate, propyl phenylphosphonate, phenyl propylphosphonate, isopropyl phenylphosphonate, phenyl isopropylphosphonate, butyl phenylphosphonate,
Phenyl butylphosphonate, isobutyl phenylphosphonate, phenyl isobutylphosphonate, sec-butyl phenylphosphonate, phenyl sec-butylphosphonate, tert-butyl phenylphosphonate, tert-
Phenyl butylphosphonate, hexyl phenylphosphonate, phenyl hexylphosphonate, cyclohexyl phenylphosphonate, phenyl cyclohexylphosphonate,
Octyl phenylphosphonate, phenyl octylphosphonate, 2-ethylhexyl phenylphosphonate, phenyl 2-ethylhexylphosphonate, dodecyl phenylphosphonate, phenyl dodecylphosphonate, tridecyl phenylphosphonate, phenyltridecylphosphonate, octadecyl phenylphosphonate, Phenyl octadecylphosphonate, methyl tolylphosphonate, tolyl methylphosphonate, ethyl tolylphosphonate, tolyl ethylphosphonate, isopropyl tolylphosphonate, tolyl isopropylphosphonate, butyl tolylphosphonate, tolyl butylphosphonate, cyclohexyl tolylphosphonate, cyclohexyl Tolyl phosphonate, methyl naphthyl phosphonate, naphthyl methyl phosphonate, ethyl naphthyl phosphonate, ethylphos Honsan naphthyl, naphthylphosphonic acid, isopropyl phosphonic acid naphthyl, butyl naphthylphosphonic acid, butylphosphonic acid naphthyl,
Cyclohexyl naphthylphosphonate, naphthyl cyclohexylphosphonate, methyl methoxyphenylphosphonate, methoxyphenyl methylphosphonate, methyl tolyloxyphenylphosphonate, tolyloxyphenyl methylphosphonate, methyl methoxyethylphosphonate, methoxyethyl methylphosphonate, phenoxyethylphosphonate methyl , Phenoxyethyl methylphosphonate, methyl allylphosphonate, allyl methylphosphonate, methyl benzylphosphonate, benzyl methylphosphonate, methyl biphenylphosphonate, biphenyl methylphosphonate, methyl benzyloxyethylphosphonate, benzyloxyethyl methylphosphonate, phenylphenylphosphonate Naphthyl phenyl phosphonate, phenyl naphthyl phosphonate, phenyl Chlorophenyl phosphonate, phenyl phenyl phenyl phosphonate, tolyl phenyl phosphonate, phenyl tolyl phosphonate, xyl phenyl phosphonate, phenyl xylyl phosphonate, tolyl phosphonate, naphthyl phosphonate naphthyl, chlorophenyl phosphonate chlorophenyl, xylyl phosphonate xylyl , Methoxyphenyl phenylphosphonate, Phenyl methoxyphenylphosphonate, Benzyloxyphenyl phenylphosphonate, Phenyl benzyloxyphenylphosphonate, Dimethoxyphenyl phenylphosphonate, Phenyl dimethoxyphenylphosphonate, Phenoxyphenyl phenylphosphonate, Phenylphenoxyphenylphosphonate , Methoxyethyl phenylphosphonate, phenyl methoxyethylphosphonate, Methoxypropyl phenylphosphonate, phenyl methoxypropylphosphonate, phenoxyethyl phenylphosphonate, phenyl phenoxyethyl phosphonate, phenoxypropyl phenylphosphonate, phenyl phenoxypropylphosphonate, allyl phenylphosphonate, phenyl allylphosphonate, benzyl phenylphosphonate, Phenyl benzylphosphonate, biphenyl phenylphosphonate, phenyl biphenylphosphonate, benzyloxyethyl phenylphosphonate, phenyl benzyloxyethylphosphonate, methoxyphenylphosphonate methoxyphenyl,
Benzyloxyphenyl methoxyphenylphosphonate,
Methoxyphenyl benzyloxyphenylphosphonate,
Methoxyphenylphosphonate dimethoxyphenyl, dimethoxyphenylphosphonate methoxyphenyl, ethoxyphenylphosphonate ethoxyphenyl, methoxyphenylphosphonate phenoxyphenyl, phenoxyphenylphosphonate methoxyphenyl, methoxyphenylphosphonate tolyloxyphenyl, tolyloxyphenylphosphonate methoxyphenyl , Methoxyethyl methoxyphenylphosphonate, methoxyphenyl methoxyethylphosphonate, methoxypropyl methoxyphenylphosphonate, methoxyphenyl methoxypropylphosphonate, phenoxyethyl methoxyphenylphosphonate, methoxyphenyl phenoxyethylphosphonate, phenoxypropyl methoxyphenylphosphonate, Phenoxypropylphosphonic acid methoxy Phenyl, allyl methoxyphenylphosphonate, methoxyphenyl allylphosphonate, benzyl methoxyphenylphosphonate, methoxyphenyl benzylphosphonate, biphenyl methoxyphenylphosphonate, methoxyphenyl biphenylphosphonate, benzyloxyethyl methoxyphenylphosphonate, benzyloxyethylphosphone Methoxyphenyl acid, phenoxyphenyl phenoxyphenylphosphonate, tolyloxyphenyl phenoxyphenylphosphonate, phenoxyphenyl tolyloxyphenylphosphonate, methoxyphenoxyphenyl phenoxyphenylphosphonate, phenoxyphenyl methoxyphenoxyphenylphosphonate,
Tolyloxyphenyl tolyloxyphenylphosphonate, methoxyphenoxyphenyl methoxyphenoxyphenylphosphonate, methoxyethyl phenoxyphenylphosphonate, phenoxyphenyl methoxyethylphosphonate, methoxypropyl phenoxyphenylphosphonate, phenoxyphenyl methoxypropylphosphonate,
Phenoxyethyl phenoxyphenylphosphonate, Phenoxyphenyl phenoxyethylphosphonate, Phenoxypropyl phenoxyphenylphosphonate, Phenoxyphenyl phenoxypropylphosphonate, Allyl phenoxyphenylphosphonate, Phenoxyphenyl allylphosphonate, Benzylphenoxyphenylphosphonate, Phenoxybenzylphosphonate Phenyl, phenoxyphenylphosphonate biphenyl, biphenylphosphonate phenoxyphenyl, phenoxyphenylphosphonate benzyloxyethyl, benzyloxyethylphosphonate phenoxyphenyl, methoxyethylphosphonate methoxyethyl, methoxyethylphosphonate methoxypropyl, methoxypropylphosphonate methoxyethyl , Methoxyethylphosphonic acid Noxyethyl, methoxyethyl phenoxyethylphosphonate, phenoxypropyl methoxyethylphosphonate, methoxyethyl phenoxypropylphosphonate, allyl methoxyethylphosphonate, methoxyethyl allylphosphonate, benzyl methoxyethylphosphonate, methoxyethyl benzylphosphonate, methoxyethylphosphonate Biphenyl acid, methoxyethyl biphenylphosphonate, benzyloxyethyl methoxyethylphosphonate, methoxyethyl benzyloxyethylphosphonate, phenoxyethyl phenoxyethylphosphonate, biphenyloxyethyl phenoxyethylphosphonate, phenoxyethyl biphenyloxyethylphosphonate, phenoxyethyl Naphthoxyethyl phosphonate, naphthoxyethyl phenoxy phosphonate Cyl, phenoxypropyl phenoxyethyl phosphonate, phenoxyethyl phenoxypropyl phosphonate, allyl phenoxyethyl phosphonate, phenoxyethyl allylphosphonate, benzyl phenoxyethylphosphonate, phenoxyethyl benzylphosphonate, biphenyl phenoxyethylphosphonate, biphenylphosphonate phenoxy Ethyl, benzyloxyethyl phenoxyethylphosphonate, phenoxyethyl benzyloxyethylphosphonate, allylphosphonate allyl, benzyl allylphosphonate, allyl benzylphosphonate, biphenyl allylphosphonate, allyl biphenylphosphonate, benzyloxyethyl allylphosphonate, Allyl benzyloxyethyl phosphonate, benzyl benzyl phosphonate, benzyl phosphonate Phenyl, benzyl biphenylphosphonate,
Benzyloxyethyl benzylphosphonate, Benzyloxyethylphosphonate benzyl, Biphenylphosphonate biphenyl, Biphenylphosphonate benzyloxyethyl, Benzyloxyethylphosphonate biphenyl, Benzyloxyethylphosphonate benzyloxyethyl, Benzyloxyethylphosphonate benzyloxypropyl , Benzyloxyethyl benzyloxypropylphosphonate, benzyloxypropyl benzyloxypropylphosphonate, and the like.

R ₃ and R ₄ in the formula (2) are specifically hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group. Group, hexyl group, cyclohexyl group, octyl group, 2-ethylhexyl group, dodecyl group,
Tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, phenyl group, naphthyl group, chlorophenyl group, difluorophenyl group, tolyl group, ethylphenyl group, tert-butylphenyl group, cyclohexylphenyl group, tetradecylphenyl group, benzylphenyl Group, xylyl group, methyl, ditert-butylphenyl group, diisopropylphenyl group, methoxyphenyl group,
Ethoxyphenyl group, tert-butoxyphenyl group,
Isopropylphenyl group, benzyloxyphenyl group,
Dimethoxyphenyl group, phenoxyphenyl group, tolyloxyphenyl group, methoxyphenoxyphenyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, Examples thereof include phenoxyethyl group, biphenoxyethyl group, naphthoxyethyl group, phenoxypropyl group, biphenoxypropyl group, naphthoxypropyl group, allyl group, benzyl group, biphenyl group, benzyloxyethyl group and benzyloxypropyl group.

X in the formula (2) is specifically a single bond.
-CH₂O-,-(CH₂)_FourO-,-(CH₂)_FiveO
-,-(CH₂)₈O-,-(CH₂)_TenO-,-{(C
H₂) ₂O}₂-,-(CH₂O)_Four-,-{(CH₂)
_FiveO}_Four-,-{(CH₂)_TenO}_Four-And the like.

The resin to which the present invention is applied is not particularly limited, and examples of thermosetting resins include urethane resins, epoxy resins, polyolefin resins, polyene-polythiol resins, unsaturated polyester resins, phenol resins, furan resins and xylene resins. , Formaldehyde resin, ketone resin, urea resin, melamine resin, aniline resin, sulfonamide resin, alkyd resin, and composite resins thereof.

Examples of the thermoplastic resin include polyolefin resin, polycarbonate resin, thermoplastic polyester resin, polyether resin, polyamide resin, polyimide resin, urethane resin, polyvinyl ketone resin, polyvinyl ether resin, and composite resins thereof. .

The molding method is appropriately selected depending on the characteristics of the resin. Generally, the thermosetting resin is molded by the mold polymerization method, the compression molding method and the like, and the thermoplastic resin is molded by the injection molding method, the extrusion molding method and the like. However, the present invention can be implemented by either method. In the case of template polymerization, it is carried out by adding an acidic phosphonic acid derivative to a monomer or a mixture of monomers in advance and then polymerizing it in the template.

In other molding methods, resin powder or pellets are used for molding. After mixing the resin powder with an acidic phosphonic acid derivative, the resin powder is melted or plasticized and injected into a mold, or resin powder is molded. Any method such as a method in which an acidic phosphonic acid derivative is added at the time of manufacturing the body or pellets and the obtained resin powder or pellets are directly subjected to molding may be used.

The amount of the acidic phosphonic acid derivative used is preferably 0.001 to 20% by weight, and particularly preferably 0.01 to 5% by weight, based on the total amount of the resin. 0.001% by weight
If it is less than 20% by weight, releasability tends to decrease.
If the amount is larger, there is a concern that the physical properties of the resin may be affected.

As the mold material, generally used stainless steel, copper, aluminum and alloys thereof, wood, ceramics, glass and the like can be used.

The invention will now be described in more detail for some representative resins. As the urethane resin to be the subject of the present invention, one or more iso (thio) cyanate compounds and polyol compounds selected from polyisocyanate compounds, polyisothiocyanate compounds, and isothiocyanate compounds having an isocyanato group, A resin obtained by polymerizing one or more active hydrogen compounds selected from the group consisting of polythiol compounds and hydroxythiol compounds can be mentioned, and a known chain extender depending on the purpose during polymerization molding. , Cross-linking agent, light stabilizer,
Various additives such as an ultraviolet absorber, an antioxidant, an oil-soluble dye, a filler and a polymerization catalyst may be added.

Examples of the polyisocyanate compound include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2 '. -Dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-
1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato- 4-isocyanatomethyl octane, 2,5,7-trimethyl-
1,8-diisocyanato-5-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, 1,4-butylene glycol dipropyl ether-α, α'-diisocyanate, lysine di Isocyanate methyl ester, lysine triisocyanate, 2-isocyanatoethyl-2,6
-Diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate, xylylene diisocyanate, bis (isocyanatoethyl)
Benzene, bis (isocyanatopropyl) benzene,
α, α, α ', α'-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, messy Tyrilene triisocyanate,
Aliphatic polyisocyanates such as 2,6-di (isocyanatomethyl) furan, isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyl Dimethyl methane diisocyanate, 2,
2'-Dimethyldicyclohexylmethane diisocyanate, bis (4-isocyanato-n-butylidene) pentaerythritol, diisocyanate diisocyanate, 2-isocyanatomethyl-3- (3-isocyanatopropyl)-
5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-
2- (3-isocyanatopropyl) -5-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl)-
6-isocyanatomethyl-bicyclo [2,2,1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -5- (2-isocyanatoethyl) -bicyclo- [2,2,2 1] -heptane, 2-isocyanatomethyl-3- (3-isocyanatopropyl) -6- (2
-Isocyanatoethyl) -bicyclo- [2,2,1]-
Heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -5- (2-isocyanatoethyl)-
Bicyclo- [2,2,1] -heptane, 2-isocyanatomethyl-2- (3-isocyanatopropyl) -6-
(2-Isocyanatoethyl) -bicyclo- [2,2,
1] -heptane, 2,5 (or 6) -bis (isocyanatomethyl) -bicyclo [2,2,1] -heptane and other alicyclic polyisocyanates, phenylene diisocyanates, tolylene diisocyanates, ethyl Phenylene diisocyanate, isopropyl phenylene diisocyanate, dimethyl phenylene diisocyanate, diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate , Biphenyl diisocyanate, tolidine diisocyanate,
4,4'-diphenylmethane diisocyanate, 3,
3'-dimethyldiphenylmethane-4,4'-diisocyanate, bibenzyl-4,4'-diisocyanate,
Bis (isocyanatophenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, triphenylmethane triisocyanate, polymeric
MDI, naphthalene triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, 4-methyldiphenylmethane-3,5,2 ',
4 ', 6'-pentaisocyanate, phenylisocyanatomethylisocyanate, phenylisocyanatoethylisocyanate, tetrahydronaphthalene diisocyanate, hexahydrobenzene diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, Diphenyl ether diisocyanate, ethylene glycol diphenyl ether diisocyanate, 1,3
-Aromatic polyisocyanates such as propylene glycol diphenyl ether diisocyanate, benzophenone diisocyanate, diethylene glycol diphenyl ether diisocyanate, dibenzofurandiocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate and dichlorocarbazole diisocyanate. .

Examples of the polyisocyanate compound containing a sulfur atom include thiodiethylene diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethyl sulfone diisocyanate, dithiodimethyl diisocyanate and dithiodiethyl. Sulfur-containing aliphatic isocyanate such as diisocyanate and dithiodipropyl diisocyanate, diphenyl sulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy- Aromatic having a sulfide bond such as 4,4'-diisocyanate dibenzyl thioether, bis (4-isocyanatomethylphenyl) sulfide, 4,4'-methoxyphenylthioethylene glycol-3,3'-diisocyanate Isocyana , Diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyl diphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyl diphenyl disulfide -5,
5'-diisocyanate, 3,3'-dimethyldiphenyldisulfide-6,6'-diisocyanate, 4,
4'-Dimethyldiphenyldisulfide-5,5'-diisocyanate, 3,3'-dimethoxydiphenyldisulfide-4,4'-diisocyanate, 4,4'-dimethoxydiphenyldisulfide-3,3'-diisocyanate Aromatic isocyanate having disulfide bond such as nato, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidine sulfone-4,4'-diisocyanate, diphenylmethane Sulfone-4,4'-diisocyanate, 4-methyldiphenyl sulfone-2,4'-
Diisocyanate, 4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatobenzyldisulfone, 4,4'-dimethyldiphenylsulfone-3 , 3 '
-Diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate,
4,4'-methoxyphenylethylene sulfone-3,
Aromatic isocyanate having sulfone bond such as 3'-diisocyanate and 4,4'-dicyclodiphenylsulfone-3,3'-diisocyanate, 4-methyl-3
-Isocyanatophenylsulfonyl-4'-isocyanatophenol ester, 4-methoxy-3-isocyanatophenylsulfonyl-4'-isocyanatophenol ester and other aromatic isocyanate having a sulfonic acid ester bond, 4-methyl-3 -Isocyanatophenylsulfonylanilide-3'-methyl-4'-isocyanate, diphenylsulfonyl-ethylenediamine-
4,4'-diisocyanate, 4,4'-methoxyphenylsulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanatophenylsulfonylanilide-4-methyl-3'-isocyanate Examples thereof include aromatic isocyanates having a sulfonic acid amide bond, sulfur-containing heterocyclic compounds such as thiophene-2,5-diisocyanate, and 1,4-dithiane-2,5-diisocyanate.

As the polyisothiocyanate compound,
For example, 1,2-diisothiocyanatoethane, 1,3-
Diisothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane, p
An aliphatic polyisothiocyanate such as phenylene diisopropylidene diisothiocyanate, an aliphatic isothiocyanate such as cyclohexane diisothiocyanate,
1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5
-Diisothiocyanato-m-xylene, 4,4-diisothiocyanato-1,1'-biphenyl, 1,1'-methylenebis (4-isothiocyanatobenzene), 1,1 '
-Methylenebis (4-isothiocyanato-2-methylbenzene), 1,1'-methylenebis (4-isothiocyanato-3-methylbenzene), 1,1 '-(1,2-ethanediyl) bis (4-isothiocyanatobenzene) ),
4,4'-diisothiocyanatobenzophenone, 4,
4'-diisothiocyanato-3,3'-dimethylbenzophenone, benzanilide-3,4'-diisothiocyanate, diphenyl ether-4,4'-diisothiocyanate, diphenylamine-4,4'-diisocyanate Such as aromatic polyisothiocyanate, 2,4,6-
Heterocyclic ring-containing isothiocyanates such as triisothiocyanato-3,5-triazine, and further hexanedioil diisothiocyanate, nonanedioyl diisothiocyanate, carbonic diisothiocyanate, 1,3-benzenecarbonyldiisothiate. Carbonyl isothiocyanates such as ocyanate, 1,4-benzenecarbonyldiisothiocyanate and (2,2′-bipyridine) -4,4′-dicarbonyldiisothiocyanate can be mentioned.

Further, as a polyisothiocyanate containing one or more sulfur atoms in addition to the isothiocyanato group,
For example, sulfur-containing aliphatic polyisothiocyanate such as thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), and dithiobis (2-isothiocyanatoethane), 1-isothiocyanato-4-{(2
-Isocyanato) sulfonyl} benzene, thiobis (4
-Isothiocyanatobenzene), sulfonylbis (4-
Isothiocyanatobenzene), sulfinylbis (4-
Isothiocyanatobenzene), dithiobis (4-isothiocyanatobenzene), 4-isothiocyanato-1-
{(4-isocyanatophenyl) sulfonyl} -2-methoxy-benzene, 4-methyl-3-isothiocyanatobenzenesulfonyl-4'-isocyanatophenyl ester, 4-methyl-3-isothiocyanatobenzenesulfonylanilide- Sulfur-containing aromatic polyisothiocyanate such as 3'-methyl-4'-isocyanate, thiophenone-2,5-diisothiocyanate, 1,4-dithiane-
Examples include sulfur-containing heterocyclic compounds such as 2,5-diisothiocyanate.

Further, examples of the isothiocyanate compound having an isocyanato group include 1-isocyanato-3-isothiocyanatopropane and 1-isocyanato-
5-isothiocyanatopentane, 1-isocyanato-6
Aliphatic or alicyclic compounds such as isothiocyanatohexane, isothiocyanatocarbonylisocyanate, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl- Aromatic compounds such as 3-isothiocyanato-1-isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, and further 4-isothiocyanato-4 '-Isothiocyanatodiphenyl sulfide, 2-
In addition to isothiocyanato groups such as isothiocyanato-2′-isothiocyanatodiethyl disulfide, compounds containing a sulfur atom and the like can be mentioned.

Further, halogen-substituted compounds such as chlorine-substituted compounds and bromine-substituted compounds of these iso (thio) cyanate compounds,
Furthermore, these burette reaction products, adduct reaction products with trimethylolpropane, dimerization or trimerization reaction products and the like can also be used. These may be used alone or in combination of two or more.

Examples of the polyol compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, 1,2-methylglucoside, pental. Erythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dorsitol, iditol, glycol, inositol, hexanetriol, triglycerose, diglycerol, triethylene glycol, polyethylene glycol, Tris (2-hydroxyethyl) isocyanurate, Black butanediol, cyclopentane diol, cyclohexane diol, cycloheptane diol, cyclooctane diol, cyclohexane dimethanol, hydroxypropyl cyclohexanol, tricyclo [5,2,1,0,2,6] decane -
Dimethanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,3]
1,1] dodecanediol, bicyclo [4,3,0] nonanedimethanol, tricyclo [5,3,1,1] dodecane-diethanol, hydroxypropyltricyclo [5,3,1,1] dodecanol, spiro [ 3,4] octanediol, butylcyclohexanediol, 1,
Aliphatic polyols such as 1'-bicyclohexylidenediol, cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol , Trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di (2
-Hydroxyethoxy) benzene, bisphenol A-
Bis- (2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-
In addition to aromatic polyols such as bis- (2-hydroxyethyl ether), halogenated polyols such as dibromoneopentyl glycol, polymer polyols such as epoxy resin, oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid Acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, 2-
Bromoglycol, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid, a condensation reaction product of an organic acid such as bromophthalic acid and the polyol, an addition reaction product of the polyol and an alkylene oxide such as ethylene oxide or propylene oxide, Addition reaction products of alkylene polyamines with ethylene oxide, alkylene oxides such as propylene oxide, and further bis- [4- (hydroxyethoxy)
Phenyl] sulfide, bis- [4- (2-hydroxypropoxy) phenyl] sulfide, bis- [4-
(2,3-Dihydroxypropoxy) phenyl] sulfide, bis- [4- (4-hydroxycyclohexyloxy) phenyl] sulfide, bis- [2-methyl-4-]
(Hydroxyethoxy) -6-butylphenyl] sulfide and compounds obtained by adding an average of 3 molecules or less of ethylene oxide and / or propylene oxide per hydroxyl group to these compounds, di- (2-hydroxyethyl)
Sulfide, 1,2-bis- (2-hydroxyethylmercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,4-dithiane-2,5-diol, bis (2,3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thiabutyl) methane, bis (4-hydroxyphenyl) sulfone (trade name bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S, 4,4'-thiobis (6-te
Examples thereof include polyols containing a sulfur atom such as rt-butyl-3-methylphenol) and 1,3-bis (2-hydroxyethylthioethyl) -cyclohexane.

Examples of the polythiol compound include methanedithiol, 1,2-ethanedithiol,
1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3
-Propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-
Dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo [2,2,2
1] pepta-exo-cis-2,3-dithiol,
1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester),
2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1, 3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), Trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethyl thio) -
3-mercaptopropane) and other aliphatic polythiols,
1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene,
1,4-bis (mercaptoethyl) benzene, 1,2-
Bis (mercaptomethyleneoxy) benzene, 1,3-
Bis (mercaptomethyleneoxy) benzene, 1,4-
Bis (mercaptomethyleneoxy) benzene, 1,2-
Bis (mercaptoethyleneoxy) benzene, 1,3-
Bis (mercaptoethyleneoxy) benzene, 1,4-
Bis (mercaptoethyleneoxy) benzene, 1,2,
3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene,
1,2,3-tris (mercaptomethyl) benzene,
1,2,4-tris (mercaptomethyl) benzene,
1,3,5-tris (mercaptomethyl) benzene,
1,2,3-tris (mercaptoethyl) benzene,
1,2,4-tris (mercaptoethyl) benzene,
1,3,5-tris (mercaptoethyl) benzene,
1,2,3-Tris (mercaptomethyleneoxy) benzene, 1,2,4-tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,2,3-tris ( Mercaptoethyleneoxy) benzene, 1,2,4-tris (mercaptoethyleneoxy) benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene, 1,2,3
4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3 , 5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis (mercaptoethyl) benzene, 1,2,3,
5-tetrakis (mercaptoethyl) benzene, 1,
2,4,5-Tetrakis (mercaptoethyl) benzene, 1,2,3,4-Tetrakis (mercaptoethyl)
Benzene, 1,2,3,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3
4-tetrakis (mercaptoethyleneoxy) benzene, 1,2,3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptoethyleneoxy) benzene, 2,2'-dimercaptobiphenyl , 4,4'-dimercaptobiphenyl,
4,4'-dimercaptobibenzyl, 2,5-toluenedithiol 3,4-toluenedithiol, 1,4-naphthalenedithiol, 1,5-naphthalenedithiol,
2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracene dimethanethiol, 1 , 3
-Di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4
-Aromatic polythiols such as di (p-mercaptophenyl) pentane, and 2,5-dichlorobenzene-1,3
-Dithiol, 1,3-di (p-chlorophenyl) propane-2,2-dithiol, 3,4,5-tribromo-
1,2-Dimercaptobenzene, 2,3,4,6-tetrachloro-1,5-bis (mercaptomethyl) benzene and other chlorine-substituted compounds, bromine-substituted and other halogen-substituted aromatic polythiols, and 2-methyl Amino-4,6-dithiol-sym-triazine, 2-ethylamino-4,6
-Dithiol-sym-triazine, 2-amino-4,
6-dithiol-sym-triazine, 2-morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym-triazine, 2-methoxy-4,6-dithiol-sym-
Triazine, 2-phenoxy-4,6-dithiol-s
ym-triazine, 2-thiobenzeneoxy-4,6-
Heterocyclic ring-containing polythiols such as dithiol-sym-triazine and 2-thiobutyloxy-4,6-dithiol-sym-triazine, 1,2-bis (mercaptomethylthio) benzene, and 1,3-bis (mercapto). Methylthio) benzene, 1,4-bis (mercaptomethylthio) benzene, 1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio)
Benzene, 1,2,3-tris (mermercaptomethylthio) benzene, 1,2,4-tris (mermercaptomethylthio) benzene, 1,3,5-tris (mermercaptomethylthio) benzene, 1,2,3- Tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4
-Tetrakis (mercaptomethylthio) benzene, 1,
2,3,5-tetrakis (mercaptomethylthio) benzene, 1,2,4,5-tetrakis (mercaptomethylthio) benzene, 1,2,3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3 5-tetrakis (mercaptoethylthio) benzene, 1,2,4,5
-Tetrakis (mercaptoethylthio) benzene, etc., and aromatic polythiols containing a sulfur atom in addition to the mercapto group of these alkylated products, bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) Sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropyl) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2- (2-mercaptoethylthio) Ethane,
1,2- (3-mercaptopropyl) ethane, 1,3-
Bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3
-Tris (mercaptomethylthio) propane, 1,2,
3-tris (2-mercaptoethylthio) propane,
1,2,3-Tris (3-mercaptopropylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl)
Methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane,
2,5-bis (mercaptomethyl) -1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, etc., and esters of these thioglycolic acid and mercaptopropionic acid , Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxy Propyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2
-Mercaptoacetate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2-mercaptoacetate), hydroxyethyldisulfidebis (3-mercaptopropionate), hydroxypropyldisulfidebis (2-mercapto) Acetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane- 2,5-diol bis (2-mercaptoacetate), 1,4-dithiane-2,5-diol bis (3-
Mercaptopropionate), thioglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester),
Dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 4,4-dithiodibutyric acid bis (2-
Mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2,3-dimercaptopropyl ester) ), Dithiodipropionic acid (2,3-
Aliphatic polythiol containing sulfur atom in addition to mercapto group such as dimercaptopropyl ester), 3,4-thiophenedithiol, 2,5-dimercapto-1,3
Heterocyclic compounds containing a sulfur atom in addition to the mercapto group such as 4-thiadiazole may be mentioned.

Examples of the hydroxy thiol compound include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane and 2,4-dimercapto. Phenol, 2-
Mercaptohydroquinone, 4-mercaptophenol, 3,4-dimercapto-2-propanol, 1,3
-Dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,
3-butanediol, pentaerythritol tris (3
-Mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), pentaerythritol pentakis (3-mercaptopropionate) ), Hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3-
Mercaptoethylthiobenzene, 4-hydroxy-4 '
-Mercaptodiphenyl sulfone, 2- (2-mercaptoethylthio) ethanol, dihydroxyethyl sulfide mono (3-mercaptopropionate) dimercaptoethane mono (sulfylate), hydroxyethylthiomethyl-tris (mercaptoethylthio) methane, etc. Can be mentioned.

Further, a chlorine-substituted product or a bromine-substituted product of these active hydrogen compounds may be used.
These may be used alone or in combination of two or more.

The ratio of these iso (thio) cyanate compound and active hydrogen compound used is (NCO + NCS) /
The (OH + SH) functional group molar ratio is usually within the range of 0.5 to 3.0, preferably within the range of 0.5 to 1.5.

The method for molding the urethane resin is usually
The template polymerization method and the reaction injection molding method are performed.

As a template polymerization method, for example, one or more acidic phosphonic acid derivatives are dissolved in a mixture of one or more polyisothiocyanate compounds and one or more active hydrogen compounds. Then, if necessary, defoaming operation is performed. Then, the mixture is poured into a mold and gradually heated in the range of −20 to 200 ° C., preferably room temperature to 150 ° C., and more preferably 50 to 120 ° C., and polymerized in 0.5 to 72 hours.

As the reaction injection molding method, for example, an active hydrogen compound in which an acidic phosphonic acid derivative is dissolved and an isothiocyanate compound are separately charged into a high-pressure mixer tank, mixed with a high-pressure mixer under heating, and then in a mold. Injection molding into.

The epoxy resin is a resin obtained by polymerizing a raw material containing a monomer having an epoxy group and is not particularly limited, and examples of the monomer having an epoxy group include the following.

(1) Amine type epoxy compound (Chemical formula 13)

[0040]

[Chemical 13]

An epoxy compound having a group, for example,
Amino groups and amides such as N, N, N ', N'-tetraglycidylaminodiphenylmethane, meta-N, N-diglycidylaminophenylglycidyl ether, N, N, N', N'-tetraglycidyl terephthalamide It is a compound synthesized from a compound having a group and an epihalohydrin such as epichlorohydrin, methylepichlorohydrin and epibromhydrin.

Specific examples of the compound having an amino group include diaminodiphenylmethane, metaxylylenediamine, paraxylylenediamine, metaaminobenzylamine, paraaminobenzylamine, 1,3-bisaminomethylcyclohexane and 1,4-bis. Aminomethylcyclohexane, 1,3-diaminocyclohexane, 1,4-
Examples include diaminocyclohexane, metaphenylenediamine, paraphenylenediamine, benzylamine, diaminodiphenyl sulfone, diaminodiphenyl ether, diaminodiphenyl sulfide, diaminodiphenyl ketone, naphthalenediamine, aniline, toluidine, metaaminophenol, paraaminophenol, aminonaphthol and the like.

Specific examples of the compound having an amide group include phthalamide, isophthalamide, terephthalamide, benzamide, toluamide, parahydroxybenzamide and metahydroxybenzamide.

When the compound having an amino group or an amide group has a group reactive with epihalohydrin such as a hydroxyl group, a carboxyl group or a mercapto group other than the amino group or amide group, one of the groups reactive with the epihalohydrin Some or all may react with epihalohydrin and be substituted with epoxy groups.

(2) Phenolic Epoxy Compound This type of compound can be synthesized from a phenolic compound and epihalohydrin, such as bisphenol A diglycidyl ether and Epotote YDCN-220 (a product of Toto Kasei Co., Ltd.). .

Specific examples of phenol compounds include hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol sulfone, brominated bisphenol A, novolac, cresol novolac, tetraphenylethane, triphenylethane and the like.

(3) Alcohol-based epoxy compound A compound that can be synthesized from an alcohol-based compound and epihalohydrin, such as trimethylolpropane triglycidyl ether and neopentyl glycol diglycidyl ether. Specific examples of alcohol compounds include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Polypropylene glycol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol,
Dibromoneopentyl glycol, trimethylolpropane, glycerin, pentaerythritol, polycaprolactone, polytetramethylene ether glycol, polybutadiene glycol, hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide adduct, etc. And the polyester polyols made from these polyhydric alcohols and polycarboxylic acids.

(4) Epoxy compound of unsaturated compound Cyclopentadiene diepoxide, epoxidized soybean oil,
Epoxidized polybutadiene, vinyl cyclohexene epoxide, trade name ERL-422 of Union Carbide
1, epoxidized compounds of unsaturated compounds known as ERL-4234, ERL-4299, and the like.

(5) Glycidyl ester epoxy compound A compound that can be synthesized from a carboxylic acid and epihalohydrin, such as tetrahydrophthalic acid diglycidyl ester.

Specific examples of the carboxylic acid include adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid,
Phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, het acid, nadic acid, maleic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, butanetetracarboxylic acid, benzophenone Tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3
And polyvalent carboxylic acids such as methyl-cyclohexene-1,2-dicarboxylic acid.

(6) Urethane type epoxy compound It can be synthesized from the polyhydric alcohol mentioned in (3), diisocyanate and glycidol or 3-hydroxypropylene sulfide.

Specific examples of the diisocyanate include tolylene diisocyanate and diphenylmethane-4,4'-.
Diisocyanate, hexamethylene diisocyanate,
Examples thereof include isophorone diisocyanate, xylylene diisocyanate, and naphthalene diisocyanate.

(7) Alicyclic epoxy compound 3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexenedioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro-3 , 4-epoxy) cyclohexane-meta-dioxane, alicyclic epoxy compounds such as bis (3,4-epoxycyclohexyl) adipate, and the like.

(8) Epoxy compound having unsaturated double bond Glycidyl methacrylate, glycidyl acrylate,
Allyl glycidyl ether, methacryl glycidyl ether, 4- (glycidyloxy) styrene, α-methyl-4- (glycidyloxy) styrene, 4-vinylbenzoic acid glycidyl ester, 4-isopropenylbenzoic acid glycidyl ester, 2,2′- Divinyl bisphenol A glycidyl ether, 2,2'-dipropenyl bisphenol A glycidyl ether, bis (2-vinyl benzoic acid glycidyl ester) methane, bis (2-propenyl benzoic acid glycidyl ester) methane, epoxy succinic acid diallyl ester, 3, 4-epoxy methacryloyloxytricyclo [5.2.1.2.6] decane etc. are mentioned.

These epoxy compounds may be halogen-substituted compounds with chlorine, bromine or the like, or compounds in which the epoxy group is replaced with an episulfide group. Further, these epoxy compounds may be polymerized individually or in a mixture of two or more kinds.

Further, the epoxy compound is used together with known compounds such as alcohols, phenols, thiols, carboxylic acids, carboxylic acid anhydrides, amines, amides, sulfonic acids and isocyanates which are generally classified as epoxy resin curing agents. It may be polymerized. Specific examples of these epoxy resin curing agents include alcohols such as ethylene glycol and trimethylolpropane; bisphenol A, tetrabromobisphenol A, bis (hydroxyethyl) sulfide, bis- [4- (hydroxyethoxy) phenyl]. Phenols such as sulfides; thiols such as ethanedithiol, trithioglycerin, pentaerythritol tetrakis (thioglycolate), bis (mercaptoethyl) sulfide; maleic acid, succinic acid, thiodiglycolic acid, 3,3'-thio Carboxylic acids such as dipropionic acid, phthalic acid, p-phenylenedithiodiglycolic acid; phthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, dodecyl succinic anhydride, tetrabromophthalic anhydride, methylcyclopentadiene Carboxylic anhydrides such as adducts of ene and maleic anhydride; amines such as diethylenetriamine, triethylenetetraamine, metaphenylenediamine, diaminodiphenylamine, diaminodiphenylsulfone; fatty acids and fats such as fatty acids, dimer acids and trimer acids Polyamides such as condensates with group polyamines; Sulfonic acids such as m-benzenedisulfonic acid and bis (4-sulfobenzene) disulfide; Toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate , Isocyanates such as isophorone diisocyanate; 2-mercaptoethanol, thioglycolic acid, glycolic acid, 3- (hydroxysulfoxy) propionic acid, 4 as a curing agent having two or more functional groups. Aminobenzenesulfonic acid, 4-mercaptomethyl benzenesulfonic acid, 4-aminobenzene thiophenol, 2-mercaptoethylamine, and the like.

Further, a complex of boron trifluoride and ethylamine, a salt of diazonium salt such as boron tetrafluoride or phosphorus hexafluoride, an iodonium salt, a bromonium salt or a sulfinium salt may be mentioned. These epoxy resin curing agents are 1
One kind or two or more kinds may be used at the same time.

When an epoxy compound having an unsaturated double bond is used as the epoxy compound, it may be copolymerized with a vinyl monomer such as acrylic acid ester, styrene, diallyl phthalate, diethylene glycol methacrylate, diethylene glycol bisallyl carbonate.

When an epoxy resin curing agent is used,
The molar ratio of the reactive group of the curing agent / the functional group of the epoxy group of the epoxy compound is preferably in the range of 0.1 to 2.0.

The epoxy resin molding is usually carried out by template polymerization, and the polymerization method includes a heat polymerization method and a photopolymerization method, and is appropriately selected depending on the kind of the epoxy resin.

A general method of the heat polymerization method is to add an acidic phosphonic acid derivative internal mold release agent and a polymerization catalyst to an epoxy monomer mixture, and inject the mixture into a mold in which a resin gasket and a metal or glass mold are combined. 2 to ~ 150 ℃
It is performed by heating for 30 hours.

As the polymerization catalyst in the heat polymerization method, known polymerization such as tertiary amines and salts thereof, quaternary ammonium salts, imidazoles, tin compounds, peroxides, metal carboxylates, phosphines and tetraphenylboron salts are used. The catalyst is appropriately selected depending on the type of epoxy resin.

In the case of the photopolymerization method, a known polymerization catalyst such as an acidic phosphonic acid derivative internal release agent, peroxides, onium salt of Lewis acid anion, silanol derivative aluminum chelate, etc. is added to the epoxy monomer mixture, and if necessary, a photopolymerization initiation aid. It is carried out by adding a known additive such as a sensitizer and a sensitizer, injecting the mixture into a mold in which a resin gasket and a glass mold are combined, and irradiating light of 180 to 700 nm for 0.5 to 15 minutes. In addition, known additives such as ultraviolet absorbers, antioxidants, dyes, and fillers may be added as necessary in these template polymerizations.

The polyolefin resin is a resin formed by radically polymerizing a monomer having an unsaturated double bond, and the following can be exemplified as the monomer having an unsaturated double bond. Aliphatic olefin compounds such as ethylene, propylene, vinyl chloride; styrene, α-methylstyrene, p-methylthiostyrene, m-divinylbenzene, 3,3′-divinylbiphenyl, 2- (4-vinylbenzylthio) ethanol, iso Propenylnaphthalene, 1,4-bis (4-vinylbenzylthio) benzene, 1,2-bis (4-vinylbenzylthio) ethane,
Aromatic vinyl compounds such as 2- (p-vinylphenylthio) benzothiazole and cinnamic acid p-vinylbenzyl ester; methyl acrylate, methyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, triphenylmethyl methacrylate, tribromophenyl methacrylate, isono Rubornyl methacrylate, 2-methacryloyloxymethyl thiophene, 2-
Bicyclo [2.2.1] heptane methacrylate, ethylene glycol dimethacrylate, 2,2-bis- (4
-Methacryloxyphenyl) propane, 1,1,1-trimethylolpropane triacrylate, N, N ',
N "-isocyanuric triacrylate, bis (2-methacryloylthioethyl) sulfide, 2,5-di (methacryloyloxy) -1,4-dithiane, bis (acryloxymethyl) tricyclo [5.2.1.02,6] ] Decane, S-methylthiomethacrylate, 1,2-bis (methacryloylthio) ethane, bis (methacryloylthioethyl) sulfide, 4,4′-dimercaptodiphenylsulfide dimethacrylate, and other acrylic ester compounds; acrylonitrile, methacrylonitrile ,
Unsaturated nitrile compounds such as cinnamonitrile; acrylamide compounds such as acrylamide and methacrylamide;
Allyl ester compounds such as diallyl phthalate, diallyl maleate, diallyl fumarate, allyl cinnamate and allyl benzoate; diallyl ether, bis (allyloxy) ethane, 2,2-bis (4-allyloxyphenyl) propane, 2,2- Allyl ether compounds such as bis (4-allyloxyethoxyphenyl) propane, 1,4-bis (allylthio) benzene and diarylidene pentaerythritol; diethylene glycol bisallyl carbonate, β-thiodiglycol bisallyl carbonate, 2,2- Bis [4- (2-allyloxycarbonyloxy) ethoxy-3,5-dibromophenyl]
Allyl carbonate compounds such as propane; cyclohexylmaleimide, m-octylmaleimide, phenylmaleimide, chlorophenylmaleimide, N, N '-(4
A maleimide compound such as 4′-diphenylmethane) bismaleimide, and these compounds having an unsaturated double bond may be polymerized individually or as a mixture of two or more kinds. Usually, the thermoplastic polyolefin resin is molded by injection molding, and the thermosetting polyolefin resin is molded by mold polymerization.

The conditions for template polymerization are appropriately selected depending on the monomers to be used. An acidic phosphonic acid derivative and a radical polymerization initiator are added to the raw material monomers, and if necessary, degassing is performed under reduced pressure, and the mixture is injected into the template by heat, micro It is radically polymerized by waves, infrared rays and ultraviolet rays. Radical polymerization initiators that can be used in the polymerization by heat, microwaves, infrared rays include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobisisovaleronitrile, 2,2 ′.
-Azo compounds such as azobis (2,4-dimethylvaleronitrile); ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide; isobutyryl peroxide, 2,4- Diacyl peroxides such as dichlorobenzoyl peroxide, o-methylbenzoyl peroxide, lauroyl peroxide and p-chlorobenzoyl peroxide;
Hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide and t-butyl peroxide; dicumyl peroxide, t-butyl cumyl peroxide, di Dialkyl peroxides such as -t-butyl peroxide and tris (t-butylperoxy) triazine; 1,1-di-t-butylperoxycyclohexane, 2,2-di (t-butylperoxy) butane, etc. Peroxyketals; t-butylperoxypivalide, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-
t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, Alkyl peresters such as di-t-butyl peroxytrimethyl adipate; and percarbonates such as diisopropyl peroxy dicarbonate, di-sec-butyl peroxy dicarbonate and t-butyl peroxy isopropyl carbonate. To be

Radical polymerization initiators that can be used in the polymerization by ultraviolet rays include, for example, acetophenone, 2,
2-dimethoxy-2-phenylacetophenone, 2,2
-Diethoxyacetophenone, 4'-isopropyl-2
-Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4,4'-bis (diethylamino) benzophenone, benzophenone,
Methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, benzoin , Benzoin methyl ether, benzoin ethyl ether,
Carbonyl compounds such as benzoin isopropyl ether, benzoin butyl ether, benzoin octyl ether, benzyl, benzyl dimethyl ketal, benzyl diethyl ketal and diacetyl; methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2
Anthraquinone or thioxanthone derivatives such as methylthioxanthone, 2-isopropylthioxanthone;
Examples thereof include sulfur compounds such as diphenyl disulfide and dithiocarbamate.

The amount of the radical polymerization initiator used is appropriately selected depending on the type of radical polymerization initiator, the type of raw material monomer, etc.
It is in the range of 10% by weight, preferably 0.1 to 3% by weight.

The amount of radical polymerization initiator used is 0.001
If it is less than 10% by weight, the polymerization does not proceed substantially, and if it is used in an amount of more than 10% by weight, it is not economical and foaming may occur during the polymerization, or the molecular weight of the cured product obtained by the polymerization becomes extremely small. Not preferred because of

In the case of template polymerization, the monomer composition may be polymerized and cured as it is, or depending on the purpose, it may be prepolymerized and then polymerized and cured to adjust the viscosity or reduce the shrinkage rate during polymerization. be able to.

When transparency is not particularly required, various fillers may be blended and used as needed. Examples of the filler used here include glass fiber, alumina fiber, carbon fiber, aramid fiber and the like, as well as powdery fillers such as silica, alumina, barium sulfate and titanium oxide. In addition, it goes without saying that flame retardants, dyes, pigments and the like can be used.

The polymerization temperature and the polymerization time in the template polymerization cannot be unconditionally specified because it depends on the type of radical polymerization initiator used and the amount thereof used, but the polymerization temperature is in the range of 0 to 150 ° C., preferably 20
Is in the range of 120 to 120 ° C., and the polymerization by heat is usually 10 to 3
It is carried out by gradually raising the temperature for 0 hours, and in the case of using ultraviolet rays, the polymerization can be completed by irradiation for 0.5 to 10 minutes.

Of the polyolefin resins, thermoplastic acrylic resin is shown as an example of injection molding. Homopolymers and copolymers of acrylic monomers, and copolymerization of acrylic monomers with other olefin monomers are also shown. It may be combined.

Examples of acrylic monomers include the following. As an acrylic acid compound,
Acrylic alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, bornyl acrylate, menthyl acrylate, adamantyl acrylate, tricyclodecyl acrylate, etc. Alkyl ester, phenyl acrylate, benzyl acrylate, acrylic acid aromatic ester such as naphthyl acrylate, acrylic acid halogen-substituted aromatic ester such as fluorophenyl acrylate and chlorophenyl acrylate,
Fluoromethyl acrylate, chloroethyl acrylate,
Acrylic acid halogenated alkyl esters such as bromoethyl acrylate, hydroxyalkyl esters of acrylic acid, and thioacrylic acid S- such as S-methyl thioacrylate.
There are alkyl esters and the like.

Examples of the methacrylic acid compound include alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, bornyl methacrylate, menthyl methacrylate, adamantyl methacrylate and methacrylic acid. Methacrylic acid cycloalkyl ester such as tricyclodecyl, phenyl methacrylate,
Aromatic esters of methacrylic acid such as benzyl methacrylate and naphthyl methacrylate, halogen-substituted aromatic esters of methacrylic acid such as fluorophenyl methacrylate and chlorophenyl methacrylate, halogenated methacrylate such as fluoromethyl methacrylate, chloroethyl methacrylate and bromoethyl methacrylate. Alkyl ester, methacrylic acid hydroxyalkyl ester, thiomethacrylic acid S-alkyl ester such as thiomethacrylic acid S-methyl ester, and the like.

Examples of the other olefin monomer include the following. Examples of vinyl compounds include aromatic vinyl compounds such as styrene, α-methylstyrene, α-ethylstyrene, fluorostyrene, chlorostyrene, bromostyrene, methylstyrene and methylthiostyrene, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. .

As the unsaturated dibasic acid and its derivative,
N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-octylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc.
-Substituted maleimide, dipropyl maleate, dibutyl maleate, dipropyl fumarate, dibutyl fumarate, maleic anhydride and the like.

Examples of unsaturated fatty acids and their derivatives include acrylamides such as acrylamide and N, N-dimethylacrylamide.

The injection molding conditions are appropriately selected depending on the type of resin. Generally, a mixture of an acrylic resin and an acidic phosphonic acid derivative is melted at a resin temperature of 220 to 320 ° C., and an extruder at a temperature of 50 to 150 ° C. is used. It is injected into a mold and molded and then released.

In the present invention, known additives such as antioxidants, ultraviolet absorbers, light stabilizers, colorants and fillers may be used according to the purpose.

The polyene-polythiol resin is a resin obtained by addition-polymerizing a polyene compound having two or more unsaturated double bonds in the molecule and a polythiol compound having two or more mercapto groups in the molecule.

Examples of the polyene compound used for the polyene-polythiol resin include the following. Aromatic vinyl compounds such as m-divinylbenzene, 3,3′-divinylbiphenyl, 1,4-bis (4-vinylbenzylthio) benzene, 1,2-bis (4-vinylbenzylthio) ethane, ethylene glycol di Methacrylate, ethylene glycol diacrylate, 2,
2-bis- (4-methacryloxyphenyl) propane,
Bis (2-methacryloylthioethyl) sulfide,
Acrylic ester compounds such as 2,5-di (methacryloyloxy) -1,4-dithiane, 1,2-bis (acryloylthio) ethane, bis (4-methacryloylthiophenyl) sulfide, diallyl phthalate, diallyl maleate, Allyl ester compounds such as diallyl fumarate and allyl cinnamate, diallyl ether, diallyl sulfide, bis (allyloxy) ethane, 2,2
-Bis (4-allyloxyphenyl) propane, 2,2
-Bis (4-allyloxyethoxyphenyl) propane, 1,4-bis (allylthio) benzene, diarylidene pentaerythritol, diarylidene-2,2,6,6
Allyl ether compounds such as 6-tetramethylol cyclohexane, diethylene glycol bisallyl carbonate, β-thiodiglycol bisallyl carbonate,
2,2-bis [4- (allyloxycarbonyloxy)
Allyl carbonate compounds such as phenyl] propane. You may use these polyene compounds individually or in mixture of 2 or more types.

Examples of the polythiol compound used for the polyene-polythiol resin include the following. Methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,
2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol,
2,2-dimethylpropane-1,3-dithiol, 3,
4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo [2.2.1] pepta-exo-cis-2,3-dithiol, 1,1-bis (mercaptomethyl) ) Cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3- Dimercapto-1-propanol (3-mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropylmethyl Ether, 2,2-bis (me Captomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane bis (2-mercaptoacetate) ), Trimethylolpropane bis (3
-Mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, Bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (mercaptoethylthio) ethane, 1,2-bis (mercaptopropylthio) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane 1 2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethyl thio) propane, 1,2,3-tris (3
-Mercaptopropylthio) propane, tetrakis (mercaptomethylthio) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, 2, 5-dimercapto-1,4-dithiane, 2,5-bis (mercaptomethyl) -1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide,
Bis (mercaptopropyl) disulfide and the like and their esters of thioglycolic acid and mercaptopropionic acid, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3
-Mercaptopropionate), hydroxyethylsulfide bis (2-mercaptoacetate), hydroxyethylsulfide bis (3-mercaptopropionate), hydroxypropylsulfide bis (2-mercaptoacetate), hydroxypropylsulfide bis (3-mercapto) Propionate), hydroxymethyldisulfidebis (2-mercaptoacetate), hydroxymethyldisulfidebis (3-mercaptopropionate), hydroxyethyldisulfidebis (2-
Mercaptoacetate), hydroxyethyldisulfidebis (3-mercaptopropionate), hydroxypropyldisulfidebis (2-mercaptoacetate), hydroxypropyldisulfidebis (3-mercaptopropionate), 2-mercaptoethyletherbis (2- Mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2,5-diol bis (2-
Mercaptoacetate), 1,4-dithiane-2,5-
Diol bis (3-mercaptopropionate), thioglycolic acid bis (2-mercaptoethyl ester),
Thiodipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercapto) Ethyl ester), 4,4-dithiodibutyric acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester) ), Dithioglycolic acid bis (2,3-dimercaptopropyl ester), dithiodipropionic acid bis (2,3-dimercaptopropyl ester) and other aliphatic polythiols, 1,2-dimercaptobenzene, 1,3- Dimercaptobenzene, 1,4-dimercaptobenzene, 1 2- bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene,
1,2-bis (mercaptoethyl) benzene, 1,3-
Bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2-bis (mercaptomethyleneoxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethylene) (Oxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene, 1,3-bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene,
1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1 , 2,3-Tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethyleneoxy) Benzene, 1,2,4-
Tris (mercaptomethyleneoxy) benzene, 1,
3,5-Tris (mercaptomethyleneoxy) benzene, 1,2,3-Tris (mercaptoethyleneoxy)
Benzene, 1,2,4-tris (mercaptoethyleneoxy) benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5- Tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene,
1,2,3,4-tetrakis (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3 , 4-tetrakis (mercaptoethyl) benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3,
4-tetrakis (mercaptomethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptomethyleneoxy) benzene, 1,2,3,4-tetrakis (mercaptoethyleneoxy) benzene, 1,2,3,5- Tetrakis (mercaptoethyleneoxy) benzene, 1,
2,4,5-Tetrakis (mercaptoethyleneoxy)
Benzene, 2,2'-dimercaptobiphenyl, 4,
4'-dimercaptobiphenyl, 4,4'-dimercaptobibenzyl, 2,5-toluenedithiol, 3,4-
Toluenedithiol, 1,4-naphthalenedithiol,
1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10 -Anthracene dimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-
1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane, 1,2-bis (mercaptomethylthio) benzene, 1,3-bis (mercaptomethylthio)
Benzene, 1,4-bis (mercaptomethylthio) benzene, 1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene,
1,4-bis (mercaptoethylthio) benzene, 1,
2,3-tris (mercaptomethylthio) benzene,
1,2,4-Tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethyl) Thio)
Benzene, 1,3,5-tris (mercaptoethylthio) benzene, 1,2,3,4-tetrakis (mercaptomethylthio) benzene, 1,2,3,5-tetrakis (mercaptomethylthio) benzene, 1,2, 4,5-
Tetrakis (mercaptomethylthio) benzene, 1,
2,3,4-tetrakis (mercaptoethylthio) benzene, 1,2,3,5-tetrakis (mercaptoethylthio) benzene, 1,2,4,5-tetrakis (mercaptoethylthio) benzene, and the like. Aromatic polythiols such as nuclear alkylated compounds, 2-methylamino-4,
6-dithiol-sym-triazine, 2-ethylamino-4,6-dithiol-sym-triazine, 2-amino-4,6-dithiol-sym-triazine, 2-
Morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-
sym-triazine, 2-methoxy-4,6-dithiol-sym-triazine, 2-phenoxy-4,6-dithiol-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 3, Four
Examples thereof include heterocyclic polythiol compounds such as thiophenedithiol, bismuthiol, and 2,5-dimercapto-1,3,4-thiadiazole. Furthermore, these polythiol compounds may have a substituent such as a halogen group such as chlorine and bromine, a hydroxyl group, and an amino group. These polythiol compounds may be used alone or in combination of two or more.

The mixing ratio of the polyene compound and the polythiol compound is such that the molar ratio of the mercapto group / double bond functional group is 0.
001 to 1.2, more preferably 0.01 to 1.
A range of 0 is good. When the ratio is more than 1.2, the hardness of the resulting resin becomes insufficient, and when the ratio is less than 0.001, the polyene-polythiol resin has sufficient physical properties such as high refractive index and low water absorption. It is not preferable because it is not exhibited.

For the purpose of controlling the crosslinking density, a monoolefin compound such as methyl acrylate or styrene, or a monothiol compound such as octyl mercaptan or dodecyl mercaptan may be added to the mixture of the polyene compound and the polythiol compound.

The conditions for template polymerization are appropriately selected depending on the monomers to be used, but an acidic phosphonic acid derivative and a radical polymerization initiator are added to the raw material monomers, and if necessary, degassing under reduced pressure is carried out, and the mixture is injected into the template by heat or micro It is radically polymerized by waves, infrared rays, and ultraviolet rays.

Examples of the radical polymerization initiator which can be used in the polymerization by heat, microwave and infrared rays include 2,
2'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, 2,2'-azobis (2,4-
Azo compounds such as dimethyl valeronitrile); ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide; isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, o- Diacyl peroxides such as methylbenzoyl peroxide, lauroyl peroxide and p-chlorobenzoyl peroxide; 2,4,4-trimethylpentyl-2-hydroperoxide, diisopropylbenzene peroxide, cumene hydroperoxide, t-
Hydroperoxides such as butyl peroxide; dicumyl peroxide, t-butylcumyl peroxide, di-
Dialkyl peroxides such as t-butyl peroxide and tris (t-butylperoxy) triazine; 1,1
-Di-t-butylperoxycyclohexane, 2,2-
Peroxyketals such as di (t-butylperoxy) butane; t-butylperoxypivalide, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t- Butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, di- alkyl peresters such as t-butyl peroxytrimethyl adipate; diisopropyl peroxy dicarbonate,
Examples include parkanates such as di-sec-butylperoxydicarbonate and t-butylperoxyisopropyl carbonate.

Radical polymerization initiators that can be used in the polymerization by ultraviolet rays include, for example, acetophenone, 2,
2-dimethoxy-2-phenylacetophenone, 2,2
-Diethoxyacetophenone, 4'-isopropyl-2
-Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4,4'-bis (diethylamino) benzophenone, benzophenone,
Methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, benzoin , Benzoin methyl ether, benzoin ethyl ether,
Carbonyl compounds such as benzoin isopropyl ether, benzoin butyl ether, benzoin octyl ether, benzyl, benzyl dimethyl ketal, benzyl diethyl ketal and diacetyl; methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2
Anthraquinone or thioxanthone derivatives such as methylthioxanthone, 2-isopropylthioxanthone;
Examples thereof include sulfur compounds such as diphenyl disulfide and dithiocarbamate.

The amount of the radical polymerization initiator used is appropriately selected depending on the kind of the radical polymerization initiator, the kind of the raw material monomer and the like.
It is in the range of 10% by weight, preferably 0.1 to 3% by weight. If the amount of the radical polymerization initiator used is less than 0.001% by weight, the polymerization does not substantially proceed, and if the amount used exceeds 10% by weight, it is not economical and foaming may occur during the polymerization, or the polymerization may be caused by the polymerization. This is not preferable because the molecular weight of the obtained cured product becomes extremely small.

In the case of template polymerization, the monomer composition may be polymerized and cured as it is, or depending on the purpose, it may be prepolymerized and then polymerized and cured to adjust the viscosity or reduce the shrinkage rate during polymerization. be able to.

When transparency is not particularly required, various fillers may be blended and used as needed. Examples of the filler used here include glass fiber, alumina fiber, carbon fiber, aramid fiber and the like, as well as powdery fillers such as silica, alumina, barium sulfate and titanium oxide. In addition, it goes without saying that flame retardants, dyes, pigments and the like can be used.

The polymerization temperature and the polymerization time in the template polymerization cannot be unconditionally specified because they vary depending on the type and the amount of the radical polymerization initiator used, but the polymerization temperature is in the range of 0 to 150 ° C., preferably 20
Is in the range of 120 to 120 ° C., and the polymerization by heat is usually 10 to 3
It is carried out by gradually raising the temperature for 0 hours, and in the case of using ultraviolet rays, the polymerization can be completed by irradiation for 0.5 to 10 minutes.

The polycarbonate resin is an average of homopolymers or copolymers obtained by the reaction of a dihydric phenol and a carbonylating agent such as phosgene or diphenyl carbonate, further branched ones, and ones having a long-chain alkyl group introduced at the end. Molecular weight is 12,000 to 30,0
Some of them are around 00.

Further, a modified polycarbonate resin obtained by using bisphenol or vinylphenol having a carbon-carbon unsaturated double bond as a comonomer or a terminal stopper is grafted with styrene or the like, and terephthalic acid is used as a part of phosgene. It is possible to use any one of chloride and isophthalic chloride, which partially have an ester bond, or modified polystyrene in which a phenolic hydroxyl group or the like is introduced as a comonomer and which is graft-polymerized with a polycarbonate resin. Also,
Reinforced resin composition obtained by compounding and reinforcing polycarbonate resin with glass fiber, carbon fiber, ABS resin, polyester resin such as polyethylene terephthalate, PMM
The present invention is effectively used for a resin composition such as A resin.

Here, as the dihydric phenols, 2,2
-Bis (4-hydroxyphenyl) propane, bis (4
-Hydroxyphenyl) methane, 1,2-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylmethane, 1 , 1-bis (4-
Hydroxyphenyl-1,1-diphenyl) methane,
1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and further lower alkyl groups for these phenyl groups And those in which a halogen atom is substituted are exemplified. Further, in the present invention, known antioxidants, ultraviolet absorbers, colorants, fillers and the like may be added depending on the purpose.

Examples of the polyester resin include thermosetting polyester resins such as alkyd resins and unsaturated polyester resins, and thermoplastic polyester resins represented by polyethylene terephthalate. Polyester resin is a resin formed by condensing a polybasic acid polyol,
Examples of the polybasic acid include phthalic anhydride, isophthalic acid, maleic acid, fumaric acid, sebacic acid, adipic acid, citric acid, tartaric acid, malic acid, diphenic acid, 1,8-naphthalyl acid and terephthalic acid. .. Examples of the polyol include glycerin, pentaerythritol, ethylene glycol, diethylene glycol and trimethylolpropane. Further, known antioxidants, ultraviolet absorbers, colorants, fillers and the like may be added depending on the purpose.

[0096]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. Hereinafter, Examples 1 to 43 and Comparative Examples 1 to 8
The urethane resin of 6 has a diameter of 70 mm and a thickness of 9 mm depending on the mold.
Was molded into a flat plate. The mold releasability was evaluated by marking a case where a Teflon wedge was driven between the molded product and the mold and easily releasing the mold, a case where there was resistance but the mold was released, and a case where the mold could not be released. In addition, the turbidity of the molded product is Suga Test Machine Co., Ltd.
Use a digital haze computer HGM-2DP manufactured by J
It was measured according to 6.4 of ISK7105.

Examples 1 to 43 A mixture of the polyisocyanate compound, active hydrogen compound and acidic phosphonic acid derivative shown in Table 1 (Tables 1 to 15) was poured into a glass mold and heated from 25 ° C to 120 ° C for 48 hours. The temperature was gradually raised to require template polymerization. Table 1 shows the releasability after polymerization and the haze measurement value of the urethane resin plate.
~ 15). All were easily released, and the haze of the urethane resin flat plate was small and good. Also, I did not feel particularly sick during the work.

Comparative Examples 1-86 In the same manner as in Examples 1 to 43, a known internal mold releasing agent was used instead of the acidic phosphonic acid derivative, and no mold releasing agent was used at all. The results are shown in Table 1 (Tables 1 to 15). With respect to the acidic phosphonic acid derivative of the present invention, it was not easy to release any of the known internal release agents, and the haze value of the urethane resin flat plate was high. Further, when no mold release agent was used, the mold release was not possible in any case, and the haze value could not be measured.

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

[0102]

[Table 4]

[0103]

[Table 5]

[0104]

[Table 6]

[0105]

[Table 7]

[0106]

[Table 8]

[0107]

[Table 9]

[0108]

[Table 10]

[0109]

[Table 11]

[0110]

[Table 12]

[0111]

[Table 13]

[0112]

[Table 14]

[0113]

[Table 15]

Example 44 Branched polyoxyalkylene ether polyol (OHV
28) 100 parts of 0.1 parts of triethylenediamine and 0.1 parts of dibutyltin dilaurate as a polymerization catalyst were mixed, and 5 parts of propylphenoxyphenylphosphonate as an internal mold release agent was further added to obtain a uniform solution. The amount of urethane-modified diphenylmethane diisocyanate (isocyanate content 23%) was adjusted to the above solution so that the isocyanate index was 107, and the diameter was 70 mm in the aluminum mold by the reaction injection molding method. It was formed into a flat plate having a size of 9 mm. The mold release was easy, and the haze value of the obtained flat plate was as good as 0.4%. Also, I did not feel particularly sick during the work.

Comparative Example 87 In Example 2, 0.05 part by weight of diethyl thiophosphate was used as an internal release agent. The mold releasability was good, and the haze value was as good as 0.1, but in the work of adding the internal mold release agent to the monomer in advance, I felt uncomfortable due to a strong unpleasant odor.

Comparative Example 88 In Example 20, 2 parts of zinc stearate and 3 parts of N, N, N′-tris (2-hydroxypropyl) ethylenediamine were heated to 90 to 100 ° C. as an internal mold release agent to form a uniform solution. I used what I did. The mold release was easy, but the haze value of the obtained flat plate was poor at 23.7%.

Examples 45 to 56 In the combinations of epoxy compounds and various additives shown in Table 2 (Tables 16 to 19), an acidic phosphonic acid derivative was mixed as an internal release agent, and then a resin gasket and a glass mold were mixed. It was poured into the combined molds and subjected to heat polymerization or photopolymerization to form a flat plate resin having a diameter of 70 mm and a thickness of 9 mm. During this work, I didn't feel particularly bad. The mold releasability was evaluated by marking a case where a Teflon wedge was driven between the molded product and the mold and easily releasing the mold, a case where there was resistance but the mold was released, and a case where the mold could not be released.
In addition, the turbidity of the molded product is 9 mm in thickness using a digital haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd.
The haze (fogging value) of flat-plate epoxy resin is determined by JISK7105.
It was measured according to 6.4 of the above, and was calculated to one decimal place.
The results are shown in Table 2 (Tables 16 to 19).

Comparative Examples 89 to 112 In the raw material monomer combinations of Examples, the same procedure was carried out when a known internal mold releasing agent was used in place of the acidic phosphonic acid derivative and when no mold releasing agent was used at all. And the haze value of the molded product was measured. The results are shown in Table 2 (Table 16).
~ 19). None of the known internal release agents for the acidic phosphonic acid derivative of the present invention is easy to release,
The haze value of the resin was also high. Further, when no mold release agent was used, the mold release was impossible and the haze value could not be measured.

[0119]

[Table 16]

[0120]

[Table 17]

[0121]

[Table 18]

[0122]

[Table 19]

Comparative Example 113 In Example 47, 2.0 parts of dioctyl thiophosphate was used. The release property was good and the haze value was as good as 0.1%, but in the work of adding the internal release agent to the monomer in advance, the unpleasant odor made me feel uncomfortable.

Examples 57 to 68 and Comparative Examples 114 to 13
7 Addition of an acidic phosphonic acid derivative as an internal release agent to the olefin monomer composition shown in Table 3 (Tables 20 to 23), addition of a known internal release agent, use of no release agent at all Each was subjected to mold polymerization in a mold in which a resin gasket and a glass disc were combined to prepare a flat plate molded product made of polyene-polythiol resin having a diameter of 70 mm and a thickness of 9 mm. During the work, I did not feel particularly sick. The mold releasability was evaluated as ◯ when a Teflon wedge was inserted between the molded product and the glass flat plate for easy mold release, and as x when there was resistance to the mold release. In addition, the turbidity of the molded product is confirmed by Suga Test Instruments Co., Ltd. Digital Haze Computer H
Using GM-2DP, the haze value (cloudiness value) at a thickness of 9 mm was measured according to JIS K7105, 6.4, and was calculated to one decimal place. The results are shown in Table 3 (Tables 20 to 2).
It is shown in 3).

[0125]

[Table 20]

[0126]

[Table 21]

[0127]

[Table 22]

[0128]

[Table 23]

Examples 69 to 79 and Comparative Examples 138 to 15
9 An acrylic resin having the monomer composition shown in Table 4 (Tables 24 to 27) to which an acidic phosphonic acid derivative has been added as an internal release agent, a known internal release agent has been added, and an internal release agent is not used. Each one is injection molded and has a diameter of 70
A flat plate having a thickness of 9 mm and a thickness of 9 mm was prepared. During the work, I did not feel particularly sick. The mold releasability was evaluated as ◯ when a wedge was inserted between the molded product and the mold to easily release the mold, and as × when the mold release had resistance. The haze value (cloudiness value) at a thickness of 9 mm was measured according to 6.4 of JIS K7105 using a digital haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. Asked. The results are shown in Table 4 (Table 24
~ 27).

[0130]

[Table 24]

[0131]

[Table 25]

[0132]

[Table 26]

[0133]

[Table 27]

Examples 80-89 and Comparative Examples 160-17
9. A raw material monomer composition shown in Table 5 (Tables 28 to 31) to which an acidic phosphonic acid derivative is added as an internal release agent,
A known internal mold release agent was added, and no known mold release agent was used at all. Mold polymerization was carried out in a mold combining a resin gasket and a glass disk, and the diameter was 70 mm and the thickness was 9 mm.
A flat plate molded product made of the polyene-polythiol resin was prepared. During the work, I did not feel particularly sick. The mold releasability was evaluated as ◯ when a Teflon wedge was inserted between the molded product and the glass flat plate for easy mold release, and as x when there was resistance to the mold release. In addition, turbidity of the molded product is measured by Suga Test Instruments Co., Ltd. digital haze computer HGM-2.
Using DP, the haze value (cloudiness value) at a thickness of 9 mm is calculated by JI
Measured according to 6.4 of SK7105, 1 after the decimal point
I asked for digits. The results are shown in Table 5 (Tables 28 to 31).

[0135]

[Table 28]

[0136]

[Table 29]

[0137]

[Table 30]

[0138]

[Table 31]

Examples 90 to 99 and Comparative Examples 180 to 18
5 2,2-bis (4-hydroxyphenyl) propane type polycarbonate powder having an average molecular weight of 15,000 to which internal release agents shown in Table 6 (Table 32) were added and those without addition were added at 250 ° C. After melting at a resin temperature of 270 ° C, 1
It was injected into a mold at 30 ° C. and molded into a flat plate having a diameter of 70 mm and a thickness of 9 mm. During the work, I did not feel particularly sick. The mold releasability was evaluated as ◯ when a wedge was inserted between the molds of the molded product and easily released, and as × when there was resistance to the mold release. Optical distortion of the molded product is Toshiba inspection machine SVP-1
Measured with 00, those with no distortion are ○, those with are ×
And Furthermore, the turbidity of the molded product uses a digital haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd.
The haze (cloudiness value) of flat plate resin with a thickness of 9 mm is determined according to JIS K71.
It measured according to 6.4 of 05, and it calculated | required to one decimal place. The results are shown in Table 6 (Table 32).

[0140]

[Table 32]

[0141]

INDUSTRIAL APPLICABILITY The molding method using the acidic phosphonic acid derivative of the present invention as an internal mold release agent improves the mold releasability between the resin and the mold, and the molded product may be distorted due to stress at the time of mold release The resin does not contaminate the mold surface. In addition, the transparency of the transparent resin is hardly impaired. Furthermore, the internal release agent itself has no unpleasant odor and is easy to handle.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Teruyuki Nagata 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Toatsu Chemical Co., Ltd. 1 (72) Inventor Seiji Shinkai 2-chome 13-13, Tomako, Higashi-ku, Fukuoka-shi, Fukuoka (72) Inventor Masahiro Goto 2-41-5 Ikumatsudai, Nishi-ku, Fukuoka-shi, Fukuoka

Claims (16)

[Claims] 1. An internal mold release agent containing an acidic phosphonic acid derivative. 2. An acidic phosphonic acid derivative, which is a compound represented by formula (1) (chemical formula 1): [In the formula (1), R ₁ and R ₂ may be the same or different and each represents a hydrogen atom, an alkyl residue having 1 to 20 carbon atoms, an aryl residue having 1 to 20 carbon atoms, or a carbon atom. Alkoxyalkyl residue having 1 to 20 carbon atoms, or alkylene residue having 1 to 20 carbon atoms, or 1 to 20 carbon atoms
Represents an araalkyl residue having 1 to 20 carbon atoms, an araaryl residue having 1 to 20 carbon atoms, or an araalkoxyalkyl residue having 1 to 20 carbon atoms. Or a compound represented by the formula (2) (Chemical Formula 2) [In Formula (2), X is represented by Formula (3) (Chemical Formula 3), and in Formula (3), m represents an integer of 1 to 10 and n represents an integer of 0 to 4. [Chemical 3] In formula (2), R ₃ and R ₄ may be the same or different and each is a hydrogen atom, an alkyl residue having 1 to 20 carbon atoms, an aryl residue having 1 to 20 carbon atoms, or a carbon number. Alkoxyalkyl residue having 1 to 20 carbon atoms, alkylene residue having 1 to 20 carbon atoms, araalkyl residue having 1 to 20 carbon atoms, araaryl residue having 1 to 20 carbon atoms, or 1 carbon atom Represents up to 20 araalkoxyalkyl residues. ] The internal mold release agent according to claim 1. 3. An acidic phosphonic acid derivative represented by formula (4) (formula 4): [In the formula (4), R ₅ is a hydrogen atom or a carbon number of 1 to 10
Up to an alkyl residue, or an alkoxy residue having 1 to 10 carbon atoms, or an alkylene residue having 1 to 10 carbon atoms,
Or an araalkyl residue having 1 to 10 carbon atoms, an araalkoxy residue having 1 to 10 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and p is 0 to 5
Represents the integer. R ₆ is a hydrogen atom or a carbon number of 1 to 20
Up to an alkyl residue, or an aryl residue up to 1 to 20 carbon atoms, an alkoxyalkyl residue up to 1 to 20 carbon atoms, an alkylene residue up to 1 to 20 carbon atoms, or up to 1 to 20 carbon atoms Araalkyl residue of, or 1 carbon atom
Up to 20 araaryl residues or 1 to 20 carbon araalkoxyalkyl residues. ) Or a compound represented by the formula (5) (Chemical Formula 5) [In Formula (5), X is represented by Formula (6) (Chemical Formula 6), and in Formula (6), s represents an integer of 1 to 10 and t represents an integer of 0 to 4. ] [Chemical 6] [In the formula (5), R ₇ and R ₈ may be the same or different and each is a hydrogen atom, an alkyl residue having 1 to 10 carbon atoms, or an alkoxy residue having 1 to 10 carbon atoms, or Alkylene residue having 1 to 10 carbon atoms, or 1 carbon atom
An araalkyl residue of up to 10 or an araalkoxy residue of 1 to 10 carbon atoms, a fluorine atom, a chlorine atom,
It represents a bromine atom or an iodine atom, and q and r represent an integer of 0 to 5. ] The internal mold release agent according to claim 1. 4. A resin molding method using the internal mold release agent according to claim 1. 5. The molding method according to claim 4, wherein the resin is a transparent resin. 6. The resin is urethane resin, epoxy resin, polyolefin resin, polyene-polythiol resin, unsaturated polyester resin, phenol resin, furan resin, xylene resin, formaldehyde resin, ketone resin, urea resin, melamine resin, aniline resin, The molding method according to claim 4, which is a sulfonamide resin, an alkyd resin, a polycarbonate resin, a thermoplastic polyester resin, a polyether resin, a polyamide resin, a polyimide resin, a polyvinyl ketone resin, a polyvinyl ether resin, or a composite resin thereof. 7. A resin, one or more iso (thio) cyanate compounds selected from the group consisting of polyisocyanate compounds, polyisothiocyanate compounds, and isothiocyanate compounds having an isocyanato group, a polyol compound, and a polythiol. The molding method according to claim 4, which is a urethane resin obtained by polymerizing one or more active hydrogen compounds selected from the group consisting of compounds and hydroxythiol compounds. 8. The resin is an amine-based epoxy compound, a phenol-based epoxy compound, an alcohol-based epoxy compound,
Polymerization of one or more of an unsaturated compound epoxy compound, a glycidyl ester epoxy compound, a urethane epoxy compound, an alicyclic epoxy compound, and an epoxy compound having an epoxy group and an unsaturated double bond in the same molecule. The molding method according to claim 4, which is an epoxy resin obtained by the method. 9. The epoxy resin comprises alcohols, phenols, thiols, carboxylic acids, carboxylic acid anhydrides,
The molding method according to claim 8, which is a resin using an epoxy resin curing agent selected from amines, amides, sulfonic acids, and isocyanates. 10. The resin is selected from the group consisting of an aliphatic olefin compound, an aromatic vinyl compound, an acrylic ester compound, an unsaturated nitrile compound, an acrylamide compound, an allyl ester compound, an allyl ether compound, an allyl carbonate compound and a maleimide compound. The molding method according to claim 4, which is a polyolefin resin obtained by polymerizing one kind or two or more kinds of monomers having an unsaturated double bond. 11. A resin is selected from a polyene compound selected from an aliphatic olefin compound, an aromatic vinyl compound, an acrylic ester compound, an allyl ether compound and an allyl carbonate compound, and an aliphatic polythiol, an aromatic polythiol and a heterocyclic polythiol. The molding method according to claim 4, which is a polyene-polythiol resin obtained by polymerizing a polythiol compound. 12. The internal mold release agent according to claim 1, 2 or 3 is added in an amount of 0.0 with respect to the total amount of monomers or the resin.
The molding method according to claim 4, wherein the content is 01 to 20% by weight. 13. A resin molded product obtained by the molding method according to claim 4. 14. The resin molded product according to claim 13, wherein the molded product is transparent. 15. The resin molded product according to claim 13, wherein the molded product is an optical product. 16. The resin molded product according to claim 15, wherein the molded product is a plastic lens.