JP2632115B2 - Release agent for molding in a synthetic resin mold and method for imparting release property to molded article in a synthetic resin mold using the release agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mold release agent for molding in a synthetic resin mold and a method for imparting mold releasability to a molded article in a synthetic resin mold using the mold release agent.

[0002]

2. Description of the Related Art Conventionally, as a release agent for molding in a synthetic resin mold, 1) waxes such as montan wax, carnauba wax, beeswax, petroleum wax, and modified products thereof (JP-A-54-4742, JP-A-60-18846
3) 2) Synthetic ester waxes (JP-A-55-86)
837), 3) Metallic soaps of higher fatty acids (JP-B-54)
4742), 4) Polygen-polyvinyl graft copolymer (JP-A-63-54462), 5) Siloxane oils such as polydimethylsiloxane and polyphenylsiloxane (JP-A-64-69306), 6) Polyfluoroethylene Fluoropolymers, etc., have been proposed, and as a method of imparting releasability to a molded article in a synthetic resin mold using these, kneading them into a synthetic resin or applying them to the mold surface is performed. ing.

However, the above-mentioned release agents 1) to 4) include:
Since heat resistance is inferior, it tends to be thermally decomposed when kneaded with a synthetic resin, and there is a disadvantage that gaseous substances and carbides generated thereby contaminate the surface of the mold and the surface of the molded product. Such a defect is remarkable in the so-called in-mold molding of engineering plastics such as polycarbonate which is melt-molded at a high temperature. The release agents of the above 5) and 6) have excellent heat resistance, but are poor in kneading with the synthetic resin and undergo phase separation. There is a drawback that a phenomenon, surface contamination of a molded product, and the like occur. Therefore, its use is limited to mold surface application.

[0004]

DISCLOSURE OF THE INVENTION The problem to be solved by the present invention is that a conventional release agent for molding in a synthetic resin mold and a method for imparting releasability to a molded product in a synthetic resin mold using the same are disclosed in US Pat.
Insufficient heat resistance may contaminate the mold surface or molded product surface,
Another problem is that various obstacles are caused due to poor phase-separation due to poor kneading with the synthetic resin.

[0005]

Means for Solving the Problems Thus, the present inventors have
As a result of intensive studies to solve the above-mentioned problems, a polysiloxane-polyvinyl graft copolymer having a specific structure in which a polysiloxane chain is used as a trunk component and a vinyl polymer chain is used as a branch component is obtained by vinyl polymerization of a polysiloxane with a vinyl monomer. The union is suitable as a mold release agent for molding in a synthetic resin mold, and the mold release is imparted to a molded article in a synthetic resin by adding the mold release agent in a predetermined ratio to the synthetic resin and molding in the mold. It has been found that the method is suitable.

That is, according to the present invention, a polysiloxane chain formed of a siloxane unit represented by the following formula 1 and a siloxane unit represented by the following formula 2 as a repeating unit is used as a main component, and a vinyl polymer chain is formed. A polysiloxane-polyvinyl graft copolymer as a branch component, wherein the molecular weight of the polysiloxane chain is 7000 to 500,000, and the ratio of the vinyl polymer chain is 10 to 50.
And a method for imparting releasability to a molded article in a synthetic resin mold using the mold release agent, wherein the mold release agent comprises a polysiloxane-polyvinyl graft copolymer in an amount of 1% by weight. According to.

[0007]

(Equation 1)

[0008]

(Equation 2)

[In the formulas 1 and 2, R ^{1 to} R ³ : a hydrocarbon group having a carbon atom directly bonded to a silicon atom and having the same or different, unsubstituted or substituted radically non-polymerizable group. A: a divalent organic group having a carbon atom directly bonded to a silicon atom and linked to B. B: Aromatic vinyl hydrocarbon having or not having a fluorine substituent, vinyl carboxylate, alkyl (meth)
A vinyl polymer chain obtained by vinyl polymerization of one or more vinyl monomers selected from acrylate and acrylonitrile. ]

In the formulas 1 and 2, R ^{1 to} R ³ are unsubstituted or substituted, non-radical polymerizable hydrocarbon groups having a carbon atom directly bonded to a silicon atom. Among these, examples of the unsubstituted hydrocarbon group include an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, an aralkyl group and the like. Four alkyl groups or phenyl groups are advantageously chosen. Examples of the substituted hydrocarbon group include a substituted hydrocarbon group having a halogen, an epoxy group, a cyano group, a ureido group, and the like. Among them, a γ-glycidoxypropyl group and a β- (3,4- Epoxy) cyclohexylethyl, γ-chloropropyl, trifluoropropyl and the like are advantageously selected. These unsubstituted hydrocarbon groups and substituted hydrocarbon groups can be in any ratio.

In Formula 2, A is a divalent organic group having a carbon atom directly bonded to a silicon atom and being bonded to B. A is important as a group connecting the vinyl polymer block to the polyorganosiloxane. Examples of A include an ethylene group, a propylene group, a 3-oxo-4-oxa-1,7-heptanediyl group, a 2-methyl-3-oxo-4-oxa-1,7-heptanediyl group, and a trimethylenethioxy group. And the like.

In the formula 2, B is a vinyl polymer chain obtained by vinyl polymerization of a vinyl monomer. In B, in addition to the vinyl polymer chain obtained by vinyl polymerization of a vinyl monomer having no fluorine substituent, a vinyl monomer containing a vinyl monomer having a fluorine substituent is vinyl-polymerized. And the resulting vinyl polymer chains. And here, a vinyl polymer chain obtained by vinyl polymerization of a vinyl monomer containing a vinyl monomer having a fluorine substituent is obtained by vinyl polymerization of a vinyl monomer having a fluorine substituent. In addition to the vinyl polymer chain, a vinyl polymer chain obtained by vinyl polymerization of a vinyl monomer having a fluorine substituent and a vinyl monomer having no fluorine substituent is included (hereinafter, these are referred to simply as Vinyl polymer chains).

Examples of the vinyl monomer having no fluorine substituent include: 1) alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate;
2) alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; 3) aromatic vinyl hydrocarbons such as styrene and α-methyl styrene;
4) Vinyl esters such as vinyl benzoate and vinyl acetate; 5) Acrylonitrile; among them, one or more vinyl monomers selected from aromatic vinyl hydrocarbons, alkyl (meth) acrylates and acrylonitrile And styrene, methyl (meth) acrylate, and ethyl (meth) acrylate.

Examples of the vinyl monomer having a fluorine substituent include 1) 1H, 1H, 11H-eicosafluoroundecyl acrylate, 1H, 1H-heptafluorobutyl acrylate, hexafluoroisopropyl acrylate, 1H, 1H Fluoroalkyl acrylates such as 1,5H-octafluoropentyl acrylate, 1H, 1H-pentadecafluorooctyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, and 2,2,2-trifluoroethyl acrylate;
2) 1H, 1H, 11H-eicosafluoroundecyl methacrylate, 1H, 1H-heptafluorobutyl methacrylate, hexafluoroisopropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H-pentadecafluorooctyl methacrylate Fluoroalkyl methacrylates such as 2,2,3,3,3-pentafluoropropyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate and 2,2,2-trifluoroethyl methacrylate; 2,3,3-tetrafluoropropyl-2- (trifluoromethyl) propenoate, 2,
Α-fluoroalkylacrylic acid esters such as 2,2-trifluoroethyl-2- (trifluoromethyl) propenoate, 4) α-fluoroalkylvinylcarboxylic acid esters such as 1- (trifluoromethyl) vinyl acetate, 5) vinyl fluorocarboxylates such as vinyl trifluoroacetate; 6) fluoro-substituted styrenes such as 3-fluorostyrene and 4-fluorostyrene; 7) α- such as α-trifluoromethylstyrene.
Examples thereof include fluoroalkylstyrenes, among which those having no fluorine substituent or fluoroalkyl group near the vinyl group are preferable. This is because the electron absorption of fluorine and the steric effect due to the fluoroalkyl group are less affected, and the vinyl polymerizability is excellent. When using a vinyl monomer having no fluorine substituent and a vinyl monomer having a fluorine substituent as the vinyl monomer, each having a fluorine substituent, aromatic vinyl hydrocarbon, vinyl carboxylate, alkyl 1 selected from (meth) acrylates
Those containing 2% by weight or more of two or more species are preferred.

Next, a method for producing the polysiloxane-polyvinyl graft copolymer in the present invention will be described.
First, a compound capable of forming a silanol group by hydrolysis (hereinafter referred to as a silanol group-forming compound) is hydrolyzed in an aqueous medium in the presence of a hydrolysis catalyst such as an acid or an alkali to form a silanol compound. Next, the silanol compound is polycondensed in the presence of a polycondensation catalyst such as an inorganic acid or an organic acid to form an aqueous emulsion of polysiloxane. In order to reduce the average particle size of the aqueous emulsion and form a stable aqueous emulsion of polysiloxane, a surfactant may be appropriately used in a hydrolysis reaction system of a silanol group-forming compound or a polycondensation reaction system of a silanol compound. it can. Finally, vinyl polymerization is performed by adding a vinyl monomer and a radical polymerization catalyst to the aqueous emulsion of polysiloxane to introduce a vinyl polymer chain into the polysiloxane.

Examples of the silanol group-forming compound include various alkoxysilanes, chlorosilanes, hydrogensilanes, acyloxysilanes, cyclosiloxane compounds and the like. In the present invention, a silanol group-forming compound that forms two silanol groups by hydrolysis is used as a raw material. Further, in the present invention, as described above, in order to introduce a vinyl polymer chain into the polysiloxane, a silanol group-forming compound having a functional group such as a radical polymerizable group or a thiol group in the molecule is used as the silanol group-forming compound. Is used.

The silanol group-forming compound which forms the siloxane unit represented by the formula 1 includes: 1) a silane compound such as dimethyldimethoxysilane, dimethyldichlorosilane, dimethyldihydrogensilane, or dimethylchlorosilanol; ) Siloxane compounds such as hexamethyldisiloxane and octamethylcyclotetrasiloxane; 3) γ-glycidoxypropyl-methyl-dimethoxysilane; γ-ureidopropyl-methyl-dimethoxysilane; N, N-dimethylaminopropyl-methyl. Silane compounds having a hydrocarbon group substituted by a polar group such as dimethoxysilane; and the like.

Examples of the silanol group-forming compound that forms the siloxane unit represented by the formula 2 include methacryloyloxypropyl methyl dimethoxysilane,
Vinyl methyl dimethoxysilane, allyl methyl
Examples thereof include silane compounds such as dimethoxysilane and mercaptopropyl-methyl-dimethoxysilane.

As described above, in the present invention, a polysiloxane-polyvinyl graft copolymer is produced by using, as a raw material, a silanol group-forming compound capable of forming two silanol groups by hydrolysis. For the purpose of controlling the molecular weight of the polysiloxane obtained by condensation polymerization of the compound and controlling the structure of the terminal group of the polysiloxane, a silanol group-forming compound that forms one silanol group by hydrolysis may be appropriately used. it can. The use ratio of such a silanol group-forming compound is usually 2 mol% or less, preferably 1 mol% or less as a siloxane unit in all the silanol group-forming compounds.

Examples of the silanol group-forming compound in which one silanol group is formed by hydrolysis include: 1)
Trimethylmethoxysilane, trimethylchlorosilane,
Silane compounds such as trimethyl hydrogen silane,
2) siloxane compounds such as hexamethyldisiloxane,
And the like.

In order to produce a polysiloxane-polyvinyl graft copolymer, as described above, a silanol group-forming compound is hydrolyzed in an aqueous medium, and the resulting silanol compound is polycondensed to obtain an aqueous emulsion of polysiloxane. Get. The aqueous medium used here is 30% by weight of water.
Above, preferably a homogeneous solvent containing at least 90% by weight. Examples of the solvent that can be used in combination with water include water-soluble solvents such as methanol, ethanol, isopropanol, acetone, and tetrahydrofuran.

The vinyl polymerization for forming a vinyl polymer chain is carried out by adding a radical polymerization catalyst and a vinyl monomer to an aqueous emulsion of polysiloxane and stirring the mixture under an inert gas atmosphere. The reaction at this time can be carried out at a temperature from room temperature to the boiling point of the vinyl monomer used.

Thus, an aqueous emulsion of a polysiloxane-polyvinyl graft copolymer in which a vinyl monomer is vinyl-polymerized on the polysiloxane is obtained. The present invention is not particularly limited as to the method for separating the polysiloxane-polyvinyl graft copolymer from the aqueous emulsion, but the aqueous emulsion may contain 1) an alkali such as sodium chloride, potassium chloride, potassium bromide or sodium sulfate. Metal salts, 2) water-soluble alkaline earth metal salts such as calcium chloride, magnesium chloride, etc.
A method of salting out and separating the polyvinyl graft copolymer is advantageous. One or more of the above salts 1) and 2) may be added as they are, or may be added as a concentrated aqueous solution. If necessary, the product obtained by salting out is further centrifuged, separated by filtration, removed of salts by washing with water or the like, and dried.

As apparent from the above description, the polysiloxane-polyvinyl graft copolymer of the present invention has a siloxane unit represented by the above formula 1 and a siloxane unit represented by the above formula 2 as its repeating units. And the polysiloxane chain formed as a main component and the vinyl polymer chain as a branch component. In the present invention, the ratio of the siloxane unit represented by the formula 2 to all the siloxane units in the repeating unit is not particularly limited, but the ratio is usually 10 mol% or less, preferably 4 mol% or less. The polysiloxane chain in the polysiloxane-polyvinyl graft copolymer has a molecular weight of 7000 to 500000,
It is preferable to use 20,000 to 100,000.
And the ratio of the vinyl polymer chain in the polysiloxane-polyvinyl graft copolymer is 10 to 50% by weight.

A synthetic resin which uses a polysiloxane-polyvinyl graft copolymer as a mold release agent and imparts mold release properties to a molded product obtained by in-mold molding includes a thermosetting synthetic resin and a thermoplastic synthetic resin. Included. Examples of the thermosetting synthetic resin include 1) unsaturated polyester resin, 2) polyurethane resin, 3) phenol resin, and 4) epoxy resin. Examples of the thermoplastic synthetic resin include: 1) polyolefin obtained by vinyl polymerization, polyvinyl aromatic hydrocarbon and vinyl aromatic hydrocarbon copolymer, polyacrylonitrile and acrylonitrile copolymer, poly (meth)
Acrylic acid ester and (meth) acrylic acid ester copolymer, polyvinyl halide and vinyl halide copolymer, 2) polycarbonate such as polyisopropylidenebisphenyl carbonate, 3) poly-ε-caprolactam, polyhexamethylene adipa Polyamides such as mid,
4) Polyacetal, 5) Polyphenylene ether and the like.

In order to use the release agent for in-mold molding of a synthetic resin of the present invention to impart mold releasability to a molded article in a synthetic resin mold obtained by in-mold molding, the release agent polysiloxane
When the polyvinyl graft copolymer is applied to a thermosetting synthetic resin, it is contained in an amount of 0.1 to 6 parts by weight, preferably 1 part by weight or more based on 100 parts by weight of the thermosetting synthetic resin. When the polysiloxane-polyvinyl graft copolymer as a release agent is applied to a thermoplastic synthetic resin, 0.07 to 100 parts by weight of the thermoplastic synthetic resin is used.
3 parts by weight, preferably 0.7 parts by weight or less. The present invention is not particularly limited with respect to the method of including the release agent in the synthetic resin. As such a method, 1) a method in which a release agent is added to and mixed with a synthetic resin, and melt-kneading is performed as necessary. 2) A master product of a synthetic resin containing a high concentration of the release agent is prepared. Is added to a synthetic resin and diluted so as to have a predetermined content ratio. In the present invention, the release property is improved by blending the release agent with the synthetic resin in this manner.
A synthetic resin composition suitable for in-mold molding is obtained.

A known kneading process can be applied to prepare a synthetic resin composition containing a release agent for in-mold molding of a synthetic resin of the present invention comprising a polysiloxane-polyvinyl graft copolymer. Such kneading processes include mills,
There are processes using a calendar, kneader, extruder, and the like. When the synthetic resin to be applied is a thermoplastic synthetic resin, the kneading temperature is equal to or higher than its melting point, generally 160 to
When the applied synthetic resin is a thermosetting synthetic resin, the temperature is from room temperature to 70 ° C, preferably 50 ° C or less. When kneading the release agent of the present invention into the thermosetting synthetic resin, mix it with the thermosetting synthetic resin before curing and before adding the curing catalyst, and disperse or dissolve uniformly under heating if necessary. Is preferred.

The present invention is not particularly limited with respect to the in-mold molding method to be employed, but when the synthetic resin to which the release agent is applied is a thermoplastic synthetic resin, the injection molding method is advantageous. When the synthetic resin to which the release agent is applied is a thermosetting synthetic resin, the in-mold molding methods include 1) a compression molding method using a sheet-like molding material (SMC), and 2) a bulk molding material (B).
MC), an injection molding method using a liquid molding material, a resin transfer molding method (RTM) or a resin injection molding method, 4) a reaction injection molding method (RIM), 5) a pultrusion molding method, and the like.

In the present invention, in order to impart a high degree of mold releasability to a synthetic resin molded product obtained by molding in a mold, the melting temperature of the polysiloxane-polyvinyl graft copolymer as a mold release agent should be as follows. It is preferable to use one having a temperature of 50 to 260 ° C. When a thermoplastic synthetic resin is used as a synthetic resin and an injection molding method is applied as an in-mold molding method to obtain a molded product, a mold to be applied as a polysiloxane-polyvinyl graft copolymer as a release agent is used. It is preferable to use a resin having a melting temperature not lower than the above temperature and not higher than the melting point of the thermoplastic synthetic resin. In addition, a thermosetting synthetic resin is used as the synthetic resin, and a low-pressure internal molding method such as a resin transfer molding method, a resin injection molding method, a reaction injection molding method, a pultrusion molding method, etc. is applied as an in-mold molding method. In the case of obtaining a polymer, it is preferable to use a polysiloxane-polyvinyl graft copolymer having a melting temperature of 50 to 100 ° C. higher than the temperature of the mold to be applied as a release agent. When using a thermosetting synthetic resin as the synthetic resin and applying a high-pressure in-mold molding method such as a compression molding method or an injection molding method as an in-mold molding method, and obtaining a molded product, a polysiloxane as a release agent is used. -It is preferable to use a polyvinyl graft copolymer having a melting temperature of the temperature of the applied mold ± 25 ° C.

[0030]

EXAMPLES In order to make the constitution and effect of the present invention more concrete, a synthesis example of a polysiloxane-polyvinyl graft copolymer will be described as Test Section 1 and an in-mold molding example will be described as Test Section 2. In each example, “part” represents “part by weight” and “%” represents “% by weight”. Various physical properties and characteristics were measured or evaluated as follows.

The molecular weight of the polysiloxane chain in the polysiloxane-polyvinyl graft copolymer A part of the aqueous emulsion of polysiloxane before vinyl polymerization of the vinyl monomer was taken out, tetrahydrofuran was added thereto, and the mixture was shaken and stirred. The polysiloxane was extracted. In this case, an appropriate amount of calcium chloride was added as needed in order to enhance the effect of extracting the polysiloxane from the aqueous emulsion. From the obtained polysiloxane extract, tetrahydrofuran was distilled off under reduced pressure to obtain a polysiloxane for molecular weight measurement.
The molecular weight (in terms of polystyrene) was measured using a PC.

Melting temperature The sample was placed in a melting point measuring apparatus, heated and adjusted at a rate of 1 ° C./min from the point at which the sample began to melt, and the temperature at which the entire sample was melted was measured. This was taken as the melting temperature.

Release in injection molding A cup-shaped molded product having a thickness of 4 mm, a height of 20 mm, and a bottom diameter of 63 mm was continuously formed by 30 shots. The release load for each shot was measured with a tension tester attached to the protruding plate, and the average value was determined. The smaller the release load, the better the releasability.

Mold Stain in Injection Molding At the end of 30 shots, the surface condition of the mold was observed and evaluated according to the following criteria. ：: Almost no stain is observed Δ: Stain is observed X: Stain is noticeably observed

Appearance of molded article in injection molding The appearance of the molded article at the 30th shot was observed and evaluated according to the following criteria. ：: Dirt and roughness on the surface are hardly recognized. Δ: Dirt and roughness on the surface are recognized. ×: Dirt and roughness on the surface are significantly recognized.

Releasability in Compression Molding or Resin Transfer Molding The ease of demolding when removing a molded product from a mold was evaluated according to the following criteria. ：: Demolding can be easily performed △: Demolding is slightly difficult, but shape defects such as deformation, cracks and distortion are not observed in the demolded molded product ×: Demolding is extremely difficult and demolding The above-mentioned shape defect is observed in the molded product

Mold Stain in Compression Molding or Resin Transfer Molding The surface condition of the mold was observed for each molding and evaluated according to the following criteria. ：: No stain is observed at all △: Stain is observed ×: Stain is noticeably observed

· Appearance of molded product in compression molding or resin transfer molding ○: No surface dirt, clouding, rough surface, and no shape defects such as warpage, cracking, distortion, etc. △: Surface dirt, clouding, rough surface recognized But the above-mentioned shape defects are not observed. ×: Surface dirt, cloudiness, and rough skin are observed, and the above-mentioned shape defects are observed.

Test Category 1 (Synthesis example of polysiloxane-polyvinyl graft copolymer) Synthesis example 1 100.6 g of octamethylcyclotetrasiloxane
(0.34 mol), 1.6 g of hexamethyldisiloxane
(10 mmol), 2.0 g (8.8 mmol) of γ-methacryloxypropylmethyldimethoxysilane, 1.1 g of dodecylbenzenesulfonic acid, and 315 g of ion-exchanged water
And dispersed with a homomixer. Next, this was passed through a homogenizer and uniformly emulsified to obtain 421 g of an aqueous emulsion of a silanol compound. This was charged into a flask and subjected to condensation polymerization at 80 ° C. for 5 hours. Thereafter, the mixture was gradually cooled for 16 hours, neutralized with a saturated aqueous solution of sodium carbonate, and filtered to obtain an aqueous emulsion of polysiloxane. The aqueous emulsion of polysiloxane obtained here was charged into another flask, and 1.6 g of potassium persulfate and 400 g of ion-exchanged water were added.
And heated to 70 ° C. After replacing the reaction system with nitrogen,
45 g (0.43 mol) of styrene was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was heated to 80 ° C. and aged for 4 hours.
The mixture was gradually cooled to ℃ and filtered. 10. Calcium chloride in the filtrate
After adding 6 g for salting out, the mixture was filtered, washed with 1000 g of warm water, and dried. A white powder (Example 1) was obtained. The white powdery polysiloxane-polyvinyl graft copolymer thus obtained has a polysiloxane chain having a molecular weight of about 11
000.

Synthesis Example 2 156.9 g of octamethylcyclotetrasiloxane
(0.53 mol), 1.4 g of hexamethyldisiloxane
(8.4 mmol), 3.1 g (13.5 mmol) of γ-methacryloxypropylmethyldimethoxysilane, and 1.7 g of dodecylbenzenesulfonic acid in ion-exchanged water 49
0 g, and an aqueous emulsion of polysiloxane was obtained in the same manner as in Synthesis Example 1. The aqueous emulsion of polysiloxane obtained here, potassium persulfate 0.53 g, ion exchange water 245 g, methyl methacrylate 18.2 g (0.
18 mol), and calcium chloride.
A white powder (Example 2) was obtained in the same manner as described above. The white powdery polysiloxane-polyvinyl graft copolymer thus obtained has a polysiloxane chain having a molecular weight of about 20,000.
Met.

Synthesis Example 3 162.8 g of octamethylcyclotetrasiloxane
(0.55 mol) and 6.2 g (27.0 mmol) of γ-methacryloxypropylmethyldimethoxysilane, 2.8 g of dodecylbenzenesulfonic acid, and ion-exchanged water 23
4 g, and an aqueous emulsion of polysiloxane was obtained in the same manner as in Synthesis Example 1. Aqueous emulsion of polysiloxane obtained here, 2.5 g of potassium persulfate, 967.5 g of ion-exchanged water, 82.5 g of methyl methacrylate
(0.83 mol), cyclohexyl methacrylate 8
Using 2.5 g (0.49 mol) and calcium chloride, a white powder (Example 3) was obtained in the same manner as in Synthesis Example 1. The polysiloxane-polyvinyl graft copolymer as a white powder thus obtained had a polysiloxane chain molecular weight of about 80,000.

Synthesis Example 4 An aqueous emulsion of polysiloxane was obtained in the same manner as in Synthesis Example 1. The aqueous emulsion of polysiloxane obtained here, 1.6 g of potassium persulfate, 735 g of ion-exchanged water,
A white powder (Example 4) was obtained in the same manner as in Synthesis Example 1 using 52.5 g (0.5 mol) of styrene, 52.5 g (0.99 mol) of acrylonitrile, and calcium chloride.

Synthesis Example 5 97.7 g of octamethylcyclotetrasiloxane (0.
33 mol), 4.3 g (19.6 mmol) of γ-glycidoxypropylmethyldimethoxysilane, 7.6 g of γ-methacryloxypropylmethyldimethoxysilane (3 g)
2.4 mmol) to obtain a mixed siloxane monomer. This was added to 300 g of ion-exchanged water in which 1.0 g of dodecylbenzenesulfonic acid was dissolved, dispersed by a homomixer, and further uniformly emulsified by a homogenizer to obtain an aqueous emulsion of a silanol compound. Next, 31 g of dodecylbenzene sulfonic acid and 217 g of ion-exchanged water were charged into a flask and dissolved well.
The temperature was raised to 5 ° C., and the aqueous emulsion of the silanol compound was added dropwise over 2 hours. After dropping is complete,
Aged for hours. After aging, the mixture was cooled to room temperature and neutralized with sodium carbonate to obtain an aqueous emulsion of polysiloxane. 483 g of ion-exchanged water and 1.5 g of potassium persulfate were dissolved in the aqueous emulsion of polysiloxane obtained here, transferred to another flask, and heated to 70 ° C. while flowing nitrogen. And 100 g of styrene (0.96 mol)
Was slowly added dropwise. After completion of the dropwise addition, the mixture was aged for 3 hours, and a white powder (Example 5) was obtained in the same manner as in Synthesis Example 1 using calcium chloride. The polysiloxane-polyvinyl graft copolymer as a white powder thus obtained had a polysiloxane chain molecular weight of about 67000.

Synthesis Example 6 An aqueous emulsion of the polysiloxane obtained in Synthesis Example 1 was charged into a flask, 1.6 g of potassium persulfate and 400 g of ion-exchanged water were added, and the mixture was heated to 70 ° C. After replacing the atmosphere in the flask with nitrogen, hexafluoroisopropyl acrylate 4
5 g (0.20 mol) was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was heated to 80 ° C. and aged for 4 hours. The mixture was gradually cooled to 40 ° C. and filtered. After adding 11.6 g of calcium chloride to the filtrate and salting out, it was filtered and washed with 1000 g of warm water.
Dried. A white powder (Example 6) was obtained.

Synthesis Example 7 204.2 g of octamethylcyclotetrasiloxane
(0.69 mol), 20.0 g (0.091 mol) of γ-glycidoxypropylmethyldimethoxysilane, 4.8 g of γ-methacryloxypropylmethyldimethoxysilane
(20.8 mmol), and 750 g of ion-exchanged water in which 2.5 g of dodecylbenzenesulfonic acid was dissolved.
In addition, the mixture was dispersed with a homomixer, and then uniformly emulsified with a homogenizer to obtain an aqueous emulsion of a silanol compound. Next, 77.5 g of dodecylbenzenesulfonic acid and 542.5 g of ion-exchanged water were charged into the flask, and after well dissolving, the temperature was raised to 80 to 85 ° C., and an aqueous emulsion of a silanol compound was added dropwise over 2 hours. did. After completion of the dropwise addition, the mixture was aged at 85 ° C. for 1 hour. After completion of the aging, the mixture was cooled to room temperature and neutralized with sodium carbonate to complete the polycondensation to obtain an aqueous emulsion of polysiloxane. Finally, 725 g of ion-exchanged water and 2.3 g of potassium persulfate are dissolved in the aqueous emulsion of polysiloxane obtained above, and the resultant is transferred to a flask. 224.9 g (1.61 mol) of fluoroacetate was slowly added dropwise. After completion of the dropwise addition, the mixture was aged for 3 hours, and a white powder (Example 7) was obtained in the same manner as in Synthesis Example 1 using calcium chloride. The polysiloxane-polyvinyl graft copolymer of the white powder thus obtained had a polysiloxane chain molecular weight of about 94,000.

Synthesis Example 8 97.7 g of octamethylcyclotetrasiloxane (0.
33 mol) and 1.8 g of hexamethyldisiloxane (1
1.1 mmol), 3.2 g (13.8 mmol) of γ-methacryloxypropylmethyldimethoxysilane, and 2.8 g of dodecylbenzenesulfonic acid in ion-exchanged water 234.
g, and an aqueous emulsion of polysiloxane was obtained in the same manner as in Synthesis Example 1. And the aqueous emulsion of polysiloxane obtained above, potassium persulfate 2.5
g, ion-exchanged water 967.5 g, methyl methacrylate 50.0 g (0.50 mol), 4-fluorostyrene 2
Using 5.0 g (0.20 mol) and calcium chloride,
A white powder (Example 8) was obtained in the same manner as in Synthesis Example 1. The polysiloxane-polyvinyl graft copolymer of the white powder thus obtained had a molecular weight of the polysiloxane chain of about 85,000.

Synthesis Example 9 An aqueous emulsion of the polysiloxane obtained in Synthesis Example 1 was charged into a flask, and 1.6 g of potassium persulfate, 735 g of ion-exchanged water, and 25.0 g of 4-fluorostyrene (0.2 g) were added.
Mol), acrylonitrile 25.0 g (0.47 mol)
A white powder (Example 9) was obtained in the same manner as in Synthesis Example 1 using calcium chloride and calcium chloride.

Synthesis Example 10 An aqueous emulsion of the polysiloxane obtained in Synthesis Example 5 was charged into a flask, and 483 g of ion-exchanged water, 1.5 g of potassium persulfate, and 100 g of trifluoroethyl methacrylate were added.
g (0.59 mol) and calcium chloride, and a white powder (Example 10) was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 11 An aqueous emulsion of the polysiloxane obtained in Synthesis Example 1 was charged into a flask, and 1.6 g of potassium persulfate, 400 g of ion-exchanged water, and 7.5 g (0.07 mol) of styrene were used. In the same manner as in Example 1, a viscous liquid (Comparative Example 1) was obtained.

Synthesis Example 12 An aqueous emulsion of the polysiloxane obtained in Synthesis Example 1 was charged into a flask, and 1.6 g of potassium persulfate, 400 g of ion-exchanged water, and 104 g (1 mol) of styrene were used. Similarly, a white powder (Comparative Example 2) was obtained.

The contents of the polysiloxane-polyvinyl graft copolymers obtained in Synthesis Examples 1 to 12 (Examples 1 to 10 and Comparative Examples 1 and 2) were calculated from the charge ratios of the synthetic raw materials, and the results were tabulated. 1 is shown.

[0052]

[Table 1]

In Table 1, * 1: siloxane unit represented by formula 1 / siloxane unit represented by formula 2 B-1: polystyrene block B-2: polymethyl methacrylate block B-3: methyl methacrylate / cyclohexyl methacrylate = 1 / 1 (weight ratio) copolymer block B-4: styrene / acrylonitrile = 1/1 (weight ratio) copolymer block B-5: polyhexafluoroisopropyl acrylate block B-6: polyvinyl trifluoroacetate block B-7: Copolymer block of methyl methacrylate / 4-fluorostyrene = 2/1 (weight ratio) B-8: Acrylonitrile / 4-fluorostyrene = 1
/ 1 (weight ratio) copolymer block B-9: polytrifluoroethyl methacrylate block

Test category 2 (in-mold molding example) Examples 11 to 17, Comparative Examples 3 to 11 (injection molding example) Commercially available polycarbonate resins (trade name: L-1250W, Teijin) After dry-blending sufficiently with a tumbler, extruded at 280 ° C,
Pelletized. Using the pellets, injection molding was performed under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 100 ° C., and the releasability, mold stain, and appearance of the molded product were measured or evaluated. The results are shown in Table 2.

[0055]

[Table 2]

In Table 2, the addition amount: 100 parts by weight of the polycarbonate resin relative to 100 parts by weight of the release agent R-1: ethylene glycol montanic acid R-2: polytrifluoroethylene R-3: polydimethylsiloxane (average molecular weight 1000
00) R-4: A mixture of methyl methacrylate and polydimethylsiloxane having a number average molecular weight of 5,000 having a methacryloxypropyl group at one end in a ratio of methyl methacrylate / polydimethylsiloxane = 50/50 (weight ratio). Copolymer obtained by polymerization, having a vinyl polymer chain as a trunk component and a polydimethylsiloxane chain as a branch component R-5: trimethyltrioctafluorohexylcyclotrisiloxane / hexamethyl Cyclotrisiloxane /
Hexamethyldisiloxane = 49.2 / 49.2 / 0.
JP-A-1-306, which is a condensation polymer of 63 (weight ratio)
Fluorosilicone oil obtained by the method described in Example 1 of Japanese Patent Publication No. 428 *: Could not be kneaded and could not be evaluated.

Examples 18 to 22, Comparative Examples 12 to 18
(Example of Injection Molding) After the release agent and the compounding agent shown in Table 3 were mixed with a commercially available polycaprolactam resin (trade name: UBE nylon 1013-B, manufactured by Ube Industries, Ltd.) using a blender, the mixture was kneaded and extruded with an extruder. Pellets were used. Using the pellets, injection molding was performed under the conditions of a cylinder temperature of 240 ° C. and a mold temperature of 85 ° C., and the releasability, mold stain, and appearance of the molded product were measured or evaluated. The results are shown in Table 3.

[0058]

[Table 3]

In Table 3, added amount: 100 parts by weight of polycaprolactam resin, parts by weight of release agent or compounding agent Compounding agent: plate-like talc R-6: calcium stearate

Examples 23 and 24, Comparative Examples 19 to 24
(Example of compression molding) A release agent and a compounding agent shown in Table 4 are mixed with an unsaturated polyester resin by a kneader to prepare a plate-shaped molding material (SMC) having a composition (each part by weight) shown in Table 4. did. Using this SMC, mold temperature 145 ° C, charge rate 40%,
Compression molding was performed under the conditions of a pressure of 100 kg / cm ² and a pressurization time of 180 seconds to obtain a flat molded product with ribs and bosses having a size of 500 × 1000 × 2 (thickness) mm. The releasability, mold contamination and appearance of the molded product were evaluated. The results are shown in Table 4.

[0061]

[Table 4]

In Table 4, unsaturated polyester resin: synthesized from 0.8 mol of maleic acid, 0.2 mol of isophthalic acid and 1.0 mol of propylene glycol, containing 40% by weight of styrene and having an acid value of 18.0, viscosity at 25 ° C is 1200c
ps R-7: zinc stearate Curing shrinkage inhibitor: Clayton D-1300 / Clayton G-1650 = 1/1 (weight ratio) mixture (both manufactured by Shell Chemical Co., Ltd.) Curing catalyst: t-butyl peroxybenzoate

Example 25, Comparative Examples 25 to 30 (Examples of resin transfer molding) Unsaturated polyester resin, releasing agent and compounding agent shown in Table 5 were uniformly mixed, and the composition (each weight) shown in Table 5 was obtained. Part) was prepared. A glass strand continuous mat (Unifilomat U-750, manufactured by Nippon Electric Glass Co., Ltd.) was charged into a nickel electroformed flat mold heated to 60 ° C. so as to have a glass content of 25%, and 2.5 kg / cm ^2. The mold was closed. Then, using a metering pump, the thermosetting resin liquid composition / radical initiator solution = 150/2 (50% solution of dibenzoyl peroxide as a radical initiator solution) using a metering pump. (Volume ratio), and the two solutions were uniformly mixed through a static mixer and injected into a mold. Infusion was stopped when the infusate began to flow out of the clearance opposite the inlet. 20 minutes after the injection was stopped, the mold was released to obtain a molded product. The releasability, mold stain and appearance of the molded product were evaluated. The results are shown in Table 5.

[0064]

[Table 5]

In Table 5, curing accelerator: dimethyl paratoluidine **: a uniform thermosetting resin liquid composition could not be obtained and could not be evaluated.

[0066]

As is apparent from the above description, the present invention described above has excellent mold releasability that does not impair the surface of the mold or the surface of the molded product and does not cause any trouble in the molding operation. There is an effect that it can be applied to a molded product.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number in the agency FI Technical display location // (C08L 101/00 51:08) (56) References JP-A-1-306428 (JP, A) JP-A-2-180929 (JP, A) JP-A-3-95228 (JP, A) JP-A-64-83086 (JP, A) JP-A-63-291925 (JP, A)

Claims (7)

(57) [Claims] 1. A polysiloxane chain formed of a siloxane unit represented by the following formula 1 and a siloxane unit represented by the following formula 2 as a repeating unit thereof as a main component:
And a polysiloxane having a vinyl polymer chain as a branch component.
A polyvinyl graft copolymer, wherein the polysiloxane
The molecular weight of the chain is between 7000 and 500,000;
A mold release agent for in-mold molding of a synthetic resin, comprising a polysiloxane-polyvinyl graft copolymer in which the proportion of a phenyl polymer chain is 10 to 50% by weight . (Equation 1) (Equation 2) [In the formulas 1 and 2, R ^{1 to} R ³ : a hydrocarbon group having a carbon atom directly bonded to a silicon atom and having the same or different, unsubstituted or substituted, radically non-polymerizable group. A: a divalent organic group having a carbon atom directly bonded to a silicon atom and linked to B. B: aromatics each having or not having a fluorine substituent
Vinyl hydrocarbon, vinyl carboxylate, alkyl (meth)
One or more selected from acrylates and acrylonitrile
Is a vinyl polymer obtained by vinyl polymerization of two or more vinyl monomers.
Nyl polymer chains . ] 2. A polysiloxane-polyvinyl graft copolymer
The polymer has a siloxane end group represented by the following formula 3:
The mold release agent for in-mold molding of a synthetic resin mold according to claim 1. (Equation 3) 3. The compound represented by the formula 2 wherein B is an aromatic vinyl hydrocarbon,
From alkyl (meth) acrylate and acrylonitrile
Vinyl polymerization of one or more selected vinyl monomers
The mold release agent for molding in a synthetic resin mold according to claim 1 or 2, which is a vinyl polymer chain obtained by the above method. 4. An in-mold molding comprising the mold release agent for molding in a synthetic resin mold according to claim 1, 2 or 3 in a proportion of 0.1 to 6 parts by weight based on 100 parts by weight of the thermosetting synthetic resin. A method of imparting releasability to a molded article in a synthetic resin mold. 5. The synthetic resin mold release agent according to claim 1, 2 or 3, wherein the release agent is a polyolefin, polyvinyl aromatic hydrocarbon , vinyl aromatic hydrocarbon copolymer, polyacrylonitrile , acrylonitrile copolymer, In a ratio of 0.07 to 3 parts by weight based on 100 parts by weight of a thermoplastic synthetic resin selected from (meth) acrylate , (meth) acrylate copolymer, polyvinyl halide and vinyl halide copolymer. A method of imparting releasability to a molded article of a synthetic resin mold, characterized in that the composition is contained and molded in a mold. 6. A mold release agent for molding in a synthetic resin mold according to claim 1, 2 or 3 in an amount of 0.07 to 3 parts by weight based on 100 parts by weight of a thermoplastic synthetic resin selected from polycarbonate, polyamide, polyacetal and polyphenylene ether. A method of imparting releasability to a molded article of a synthetic resin mold, characterized in that the composition is contained in a ratio of parts and molded in the mold. 7. The method according to claim 5, wherein the in-mold molding is injection molding.