JPH01282267A - Modifier for resin - Google Patents

Abstract

PURPOSE:To obtain a modifier expressed by a specified compositional formula capable of improving moldability and releasability of a resin and lubricating property of moldings thereof without reducing heat and oxidation resistance. CONSTITUTION:A modifier consisting of a polyorganosiloxane expressed by the formula [R<1> is organic group containing 3-20C polyfluoroalkyl group; R<2> is 1-6C hydrocarbon group (e.g., methyl group); R<3> is same as R<2> or 7-22C hydrocarbon group; a, b and c are >=0 and satisfy 1.9<=a+b+c<=2.2]. This modifier is blended in an amount of 0.01-30 pts.wt., preferably 0.05-10 pts.wt. with 100 pts.wt. resin or rubber.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to resin modifiers.

[Prior art and inventions to solve the problem] Silicone oil has traditionally had heat resistance, oxidation resistance, lubricity,
Due to its excellent mold releasability, it is blended with resins and rubbers to improve its molding processability and mold releasability, and is used to improve the surface lubricity and wear resistance of molded products.

However, when polydimethylsiloxane is used as silicone oil, it generally does not have sufficient compatibility with the resin.
It has been pointed out that separation or oozing from the surface of the molded product causes many problems, such as insufficient sustainability of the effect and poor paintability.

Polyorganosiloxanes containing long-chain alkyl groups or alkyl ester groups have improved compatibility, but have lower heat resistance ("Latest Applied Technology of Silicones"R&D Report No. 22 (MC (1982)).

Polyorganosiloxane having both a polyfluoroalkyl group and a 10CR group (R is a monovalent hydrogen group)
41258), the -0CR group is bonded to the silicon chain, so it is hydrolyzed and its properties are reduced. In addition, polyolcamesiloxane containing 10CR group or -0(R'-0)n group at the terminal (JP-A-82-277
Similarly, the introduced polyorganosiloxane (Japanese Patent Publication No. 44788/1988) has improved hydrolysis resistance, but its heat resistance and oxidation resistance are lower than that of polydimethylsiloxane. It is not sufficient compared to .

Furthermore, polyorganosiloxane having both a trifluoropropyl group and an organic functional group (introduced in JP-A-58-187H3) did not have sufficient lubricity.

[Means for Solving the Problems] The purpose of the present invention is to solve the above-mentioned drawbacks of the prior art. The object of the present invention is to provide a modifier that improves mold releasability and lubricating properties of molded products. That is, the present invention relates to a resin modifier made of polyorganosiloxane represented by the following average composition formula (1).

RIaR2bR3cSiOa-a-b-c
++ (I) A monovalent monovalent group containing a polyfluoroalkyl group (perfluoroalkyl group or an alkyl group in which some of the fluorine atoms of the perfluoroalkyl group are substituted with chlorine or hydrogen atoms) in the polyorganosiloxane of the present invention Organic group (
R1) is a polyfluoroalkyl group having 3 to 20 carbon atoms bonded with an alkylene group or a phenylene group, and if the number of carbon atoms in the polyfluoroalkyl group is less than this, the molding processability and mold releasability will deteriorate. The lubricating properties are insufficient, and if the amount is more than this, the compatibility with the resin will be poor. Furthermore, if there are many branches, the lubricating properties will deteriorate.

More preferably, a monovalent organic group containing a linear perfluoroalkyl group having 4 to 14 carbon atoms is used.

However, (CH2)2 is preferably used for manufacturing reasons.

R1 may be of the same kind, or different kinds of groups, such as polyfluoroalkyl groups having different numbers of carbon atoms, may be used together.

On the other hand, as the substituent (R2), a monovalent hydrocarbon group having 1 to 6 carbon atoms is used, such as methyl and ethyl.

Examples include alkyl groups such as propyl and butyl, cycloalkyl groups such as cyclohexyl, and aryl groups such as phenyl.Although these groups may be used in combination, a methyl group is preferably used in production.

Next, as the substitution 5 (R3), R2 or carbon number 7 to 2
A monovalent hydrocarbon group of No. 2 is used, but if the number of carbon atoms is larger than this, the heat resistance and oxidation resistance will decrease, and it will be difficult to obtain raw materials, which is not preferable.

The forms of hydrocarbon groups include linear, branched, ring structure,
An aromatic group or the like may be used, but preferably a linear alkyl group is employed. R3 may be of the same type, or groups having different carbon numbers or forms may be used together.

In the average composition formula, these substituents RI, R2, l (the ratio of 3 is a, b, c>0.1.9≦a+b+c≦2.2
Preferably, the F atom of the polyorganosiloxane, SiO and (R2+1(
The content (weight%) of 3) is 2.25% <F atoms <7
A range of 3% Sin<37% (R''+R3)<50% is used.

(If R2 + 1 (3) is more than 60%, heat resistance and oxidation resistance will decrease. If F atoms are less than 2.25%, the lubricating property improvement effect will be small, and if it exceeds 73%, the compatibility will be insufficient.) It will no longer be.

More preferably, 10%≦F atom≦73% Sin<37% (R”+R3) <45% range is used.

When the polyorganosiloxane of the present invention is applied to resins or rubbers, it is usually blended or added during molding, but when particularly improving the lubricating properties and mold release properties, it can be applied to the surface by methods such as impregnation, dipping, etc. A method may also be used.

Applicable resins and rubbers include polyethylene, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, polypropylene, poly(4-methylpentene),
Polystyrene, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, polymethyl methacrylate, polyvinyl chloride, vinyl chloride
Vinyl acetate copolymer, vinyl chloride vinylidene chloride copolymer, vinyl chloride acrylic ester (or methacrylic ester) copolymer, ethylene-vinyl chloride copolymer,
Propylene-vinyl chloride copolymer, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol.

Polyvinyl acetal, polyvinyl formal, polyamide, polyacetal, polycarbonate, polyester, polyphenylene oxide, polysulfone, polyarylate, polyphenylene sulfide, polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, poly(chlorotrifluoroethylene), Polyvinylidene fluoride, polyvinyl fluoride, phenolic resin, urea resin, melamine resin, xylene resin, diallyl phthalate resin, alkyd resin,
Epoxy resin, aniline resin, polyurethane, cellulose resin, silicone resin, inbrene rubber, chloroprene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, styrene-butadiene rubber, polyurethane rubber, acrylic rubber, fluororubber, silicone rubber, etc. are exemplified.

Fillers, plasticizers, heat stabilizers, antioxidants, ultraviolet absorbers, flame retardants, blowing agents,
Antistatic agents, etc. may also be added.

The polyorganosiloxane of the present invention has a resin, rubber 100%
If the amount is 5, usually o, oi to 30 parts by weight, or less than this, the effect will be small, and if it is too much, the mechanical properties of the base material will be impaired. More preferably 0.05-10
Parts by weight are used.

[Function] In the present invention, when a polyfluoroalkyl group and a long-chain alkyl group in a polyorganosiloxane are used together, they both have a higher friction reduction effect than a methyl group, and can be used on the inner side of resins and rubbers. It is thought that the lubricity is improved and the moldability is improved. It is also believed that the introduction of these groups improves the compatibility of the polyorganosiloxane with resins and rubbers, thereby reducing oozing from the surface of the molded product.

Furthermore, since the polyfluoroalkyl group is chemically inert, it is considered that it does not reduce the heat resistance or oxidation resistance of the polyorganosiloxane.

[Example] Resin used and abbreviation ■DPE (high-density polyethylene, HIZEX 250
0, Mitsui Petrochemical Co., Ltd.), ps (polystyrene, Tobolex, Mitsui Toatsu Co., Ltd.), POM (polyacetal, Duracon M90-44, Polyplastic Co., Ltd.)
, 8BS (acrylonitrile-tutadiene-styrene resin, JSRABS 38, manufactured by Japan Synthetic Rubber Co., Ltd.), p
VC (polyvinyl chloride, Takiron plate, manufactured by Takiron), PC (polycarbonate, Lexan sheet, manufactured by Asahi Glass Co., Ltd.), rppu (thermoplastic polyurethane, P-
485, manufactured by Asahi Glass Co., Ltd.).

Example 1, Comparative Examples 1 and 2.3 Modifiers (A) to (E) of the present invention, dimethylpolysiloxane (KF-96, manufactured by Shin-Etsu Chemical Co., Ltd.) and trifluoropropylmethylpolysiloxane ( FS-
1265 (manufactured by Dow Corning) was kneaded in a small kneader at 150°C for 30 minutes, and the moldability of the compounded resin was evaluated.

Modifier CH2CH2C, F9 Viscosity (A) Me3SiO(SiO)7-SiMe,
1300cste (B) II
10000cstCH2C
H□C4F9Me Akebono (C) Me+SiO+5iOhi +SiO
Piece SiMe, 100 csteMe (n/m-10/90 molar ratio) (n/m-40/60 molar ratio) Measured using a 70-tester (manufactured by Shimadzu Corporation) with a 1 mm/lam die under the conditions shown in the table below. .

HD P E 200℃ 30 kg/am2p
s zooooC10kg/cm2POM
175℃ 10 kg/c+s"HEIDON-
Type 14 (manufactured by Shinraikagakusha), ball indenter, load 400g
, measured at a friction speed of 1.7 cm/s.

(A) 1.25 2.80X 10-
23 2.91X 10-2 Example 1 5 3.37X 1O-
2(B) 3 3.28X 1O-
2(C) 1.25 2.75X to
-232,91X 10-2 Comparative Example I KF-96 (50,000 cst) 2 1.
90X101Q value: Indicates the flow rate of the resin, and the faster it is, the better the molding processability is.

Example 2.3 2 phr of the modifier (A) of Example 1 in ps and ROM
The mixture was blended at a kneading temperature of 170°C, and moldability was evaluated in the same manner as in Example 1.

P S 2.43X 10-2 1.80
X 1O-2P OM 3.30X 10-2
2.24 X 10-2 Example 4 5 g of the modifier (A) of Example 1 was placed on various synthetic resin plates.
erm'' and measured its friction coefficient.

HD P E '0.08 0.01
3A B S O,150,02P S
O,550,02P V C0150,02
5 P OM O,300,02P C0150
, 02 [-93 Bright Effects] The polyorganosiloxane of the present invention has the effect of improving the moldability and mold release properties of resins and rubbers, as well as improving the lubrication properties of molded products.

Furthermore, by increasing the content of polyfluoroalkyl groups in polyorganosiloxane, the effect of imparting properties such as oil resistance, solvent resistance, and chemical resistance to molded products is also recognized.

Claims (1)

[Claims] 1. A resin modifier made of polyorganosiloxane represented by the following average composition formula (I). R^1_aR^2_bR^3_cSiO_4_-_a_
−_b_-_c_/_2…(I) [R^1:C_3_
-_2_0 Organic group containing polyfluoroalkyl group R^2: C_1_-_6 hydrocarbon group R^3: Same as R^2 or C_7_-_2_2 hydrocarbon group a, b, c is a, b, c > 0 , 1.9≦, a+b+c≦2.2]