Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
  • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
  • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms

Definitions

• the present invention relates to a non-adhesive composition.
• Patent Document 1 International Publication No. 2004/0357078 has a polyfluoroalkyl group, and the melting point of a microcrystal derived from the polyfluoroalkyl group of a monomeric homopolymer is absent or is 55 ° C. or lower.
• Disclosed is a water-repellent and oil-repellent composition containing a polymer as an essential component.
• Patent Document 2 International Publication No. 2009/034773 describes (a) a fluoroalkyl alcohol acrylic acid derivative or a corresponding methacrylic acid derivative and (b) a monoalkyl of an acrylic acid ester or a methacrylic acid ester, fumaric acid or maleic acid. Fluorescent copolymers with esters or dialkyl esters, or vinyl esters are disclosed.
• the present inventors have made a composition containing a copolymer having a specific structure having a perfluoroalkyl group having 6 or less carbon atoms and a rubber component or a resin, thereby providing excellent mold releasability.
• the present invention was made by discovering that it has water and oil repellency. That is, the present invention provides a non-adhesive composition having excellent releasability, water repellency and oil repellency.
• the gist structure of the present invention is as follows. [1] With rubber component or resin, It contains 0.05 to 10 parts by mass of a fluorine-containing copolymer with respect to 100 parts by mass of the rubber component or resin.
• R 2 OCOCR 1 CH 2 (in the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, or an aralkyl group) (meth).
• R 1 represents a hydrogen atom or a methyl group
• R 2 represents an alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, or an aralkyl group
• meth With acrylic ester, monoalkyl ester or dialkyl ester of fumaric acid, or monoalkyl ester or dialkyl ester of maleic acid
• a non-adhesive composition which is a copolymer of.
• the non-adhesive composition of the present invention contains a rubber component or resin and a fluorine-containing copolymer of 0.05 to 10 parts by mass with respect to 100 parts by mass of the rubber component or resin.
• This fluorine-containing copolymer is a copolymer of the following monomers (a) and (b).
• R 2 OCOCR 1 CH 2
• R 1 represents a hydrogen atom or a methyl group
• R 2 represents an alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, or an aralkyl group
• the monomer (a) "fluoroalkyl alcohol (meth) acrylic acid derivative” represents a fluoroalkyl alcohol acrylic acid derivative or a fluoroalkyl alcohol methacrylic acid derivative.
• the “(meth) acrylic acid ester” which is the monomer (b) represents an acrylic acid ester or a methacrylic acid ester.
• the non-adhesive composition of the present invention contains a perfluoroalkyl group C n F 2n + 1 (n is an integer of 1 to 6) having 6 or less carbon atoms in a fluorine-containing copolymer, and a rubber component or a resin.
• a perfluoroalkyl group having 6 or less carbon atoms has low bioaccumulation, it can enhance safety to the human body.
• the fluorine-containing copolymer contains a hydrocarbon portion, it has excellent compatibility with the rubber component and the resin, and is contained in an amount of 0.05 to 10 parts by mass with respect to 100 parts by mass of the rubber component or the resin. Can also be uniformly dispersed or dissolved in the rubber component or resin.
• the surface of the non-adhesive composition is formed at the time of molding.
• the fluorine-containing copolymer exudes to form a low-energy surface.
• a non-adhesive composition containing the resin of the present invention and a fluorine-containing copolymer is filled in a mold and then crosslinked, polymerized, or the like to be molded, the surface of the non-adhesive composition is formed during the molding.
• the fluorine-containing copolymer exudes to form a low-energy surface.
• the molded product obtained by molding the non-adhesive composition can be easily taken out from the mold. Further, since the surface of the obtained molded product has low adhesion to other materials, it can have properties such as non-adhesiveness, water repellency, and oil repellency. Therefore, the molded product can be used for a product that requires these characteristics. More specifically, the molded product of the non-adhesive composition of the present invention includes rubber products such as fluororubber, natural rubber, EPDM rubber and acrylic rubber, acrylic resin, vinyl chloride resin, epoxy resin, polyurethane resin, phenol resin and the like. It can be used for applications such as resin products, waterproof sealants (modified silicones), non-adhesive and water- and oil-repellent properties of non-woven fabrics, stain prevention properties, and internal mold release agents during molding.
• rubber products such as fluororubber, natural rubber, EPDM rubber and acrylic rubber, acrylic resin, vinyl chloride resin, epoxy resin, polyurethane resin, phenol resin and
• Examples of the rubber component constituting the non-adhesive composition of the present invention include fluororubber, natural rubber, EPDM rubber, urethane rubber, acrylic rubber, hydrin rubber and the like.
• the fluororubber is not particularly limited, and examples thereof include vinylidene fluoride-based fluororubber (FKM), tetrafluoroethylene-propylene fluororubber (FEPM), tetrafluoroethylene-purple orovinyl ether-based fluororubber (FFKM), and the like. ..
• the rubber component may be either an uncrosslinked rubber component or a crosslinked rubber component, but is preferably a crosslinked rubber component.
• the crosslinked rubber component may be either a primary crosslinked or a secondary crosslinked rubber component.
• the fluororubber is distinguished from the fluoropolymer of the present invention in that it does not contain the monomer (b).
• the resin constituting the non-adhesive composition of the present invention include fluororesins, epoxy resins, phenol resins, melamine resins, polyethylene resins, polypropylene resins, polyester resins, vinyl chloride resins and the like.
• the fluororesin is distinguished from the fluorine-containing copolymer of the present invention in that it does not contain the monomer (b).
• the content of the fluorine-containing copolymer in the non-adhesive composition of the present invention is 0.05 to 10 parts by mass, but 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the rubber component or the resin. It is preferably 0.05 to 2.0 parts by mass, and even more preferably 0.05 to 1.0 parts by mass.
• the surface can be modified to be non-adhesive.
• the weight average molecular weight of the fluorine-containing copolymer is preferably 2000 to 50,000, more preferably 2000 to 20000, and even more preferably 3000 to 10000.
• the non-adhesive fluorine-containing copolymer can be transferred to the surface of the rubber component or the resin.
• the weight average molecular weight Mw of the fluorine-containing copolymer can be measured by gel permeation chromatography (GPC).
• the molar ratio of the above-mentioned monomers (a) to (b) constituting the fluorine-containing copolymer is not particularly limited, but the monomer (a) :( b) (molar ratio) is 10: 1 to 1: 1. 100 is preferable, 5: 1 to 1:50 is more preferable, and 2: 1 to 1:40 is even more preferable.
• the molar ratio of the monomers (a) to (b) is within the above range, the non-adhesive fluorine-containing copolymer can be transferred to the surface of various rubber components or resins.
• the monomer (a) 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12- Nonadecafluorododecyl acrylate, 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-Nonadecafluorododecyl methacrylate, Examples of the monomer having the following structural formula can be mentioned.
• R 2 in the above-mentioned monomer (b) in the fluorine-containing copolymer is an alkyl group, an alkoxyalkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, and is, for example, methyl, ethyl, propyl, isopropyl, n.
• -Alkyl groups such as butyl, n-hexyl, 2-ethylhexyl, n-octyl, lauryl and stearyl, and alkoxyalkyl groups such as methoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl and 3-ethoxypropyl.
• Cycloalkyl group such as cyclohexyl, aryl group such as phenyl, aralkyl group such as benzyl and the like.
• Examples of the monoalkyl ester or dialkyl ester of fumaric acid include monomethyl, dimethyl, monoethyl, diethyl, monopropyl, dipropyl, monobutyl, dibutyl, mono2-ethylhexyl, di2-ethylhexyl, monooctyl, and dioctyl of fumaric acid. Examples thereof include alkyl esters and dialkyl esters.
• Examples of the monoalkyl ester or dialkyl ester of maleic acid include monomethyl, dimethyl, monoethyl, diethyl, monopropyl, dipropyl, monobutyl, dibutyl, mono2-ethylhexyl, di2-ethylhexyl, monooctyl, and dioctyl of maleic acid. Examples thereof include alkyl esters and dialkyl esters.
• the monomer (b) examples include 2-ethylhexyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, behenyl methacrylate, cyclohexyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, behenyl acrylate, vinyl acetate, and vinyl caprylate.
• vinyl ester and monomer having a structural formula represented by the following formula can be mentioned.
• the rubber component can contain a cross-linking agent, a cross-linking accelerator, an antacid, a filler and the like as additives other than rubber.
• the resin can contain a polymerization initiator, a filler and the like.
• the monomer (a) can be produced by subjecting a fluoroalkyl alcohol to an esterification reaction with acrylic acid or methacrylic acid. Further, the fluoroalkyl alcohol can be produced from the corresponding fluoroalkyl iodide. Fluoroalkyl alcohols are obtained by first reacting fluoroalkyliodide with N-methylformamide HCONH (CH 3 ) to form a mixture of fluoroalkyl alcohol and its formate, and then hydrolyzing it in the presence of an acid catalyst. It can be manufactured by.
• the fluorine-containing copolymer of the present invention can be prepared, for example, as follows. That is, the following solvents: 1,4-bis (trifluoromethyl) benzene, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro Fluorine-containing organic solvents such as -1,3-dichloropropane, 1,1,1,2,3,4,5,5,5-decafluoropentane, perfluorohexane; methyl acetate, ethyl acetate, propyl acetate , Acetate butyl ester, ester-based solvent such as methyl acetate propionate; Ketone-based solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-hexanone; acetonitrile, dimethylformamide, diethylformamide, The polymer
• a polymerization initiator can be used.
• diacyl peroxide, peroxy carbonate, peroxy ester and the like can be used. More specifically, as the polymerization initiator, isobutyryl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, bis (heptafluorobutyryl) peroxide, pentafluorobutyroyl peroxide, bis (4-th).
• a chain transfer agent can also be used if necessary to adjust the weight average molecular weight of the fluorine-containing copolymer.
• the chain transfer agent include n-dodecyl mercaptan, dimethyl ether, methyl tertiary butyl ether, alkanes C1 to C6, methanol, ethanol, 2-propanol, cyclohexane, carbon tetrachloride, chloroform, dichloromethane, methane, ethyl acetate, and malon. Ethyl acetate, acetone and the like can be mentioned.
• the copolymerization reaction for obtaining the fluorine-containing copolymer can be carried out at a temperature of preferably 0 to 100 ° C, more preferably 5 to 60 ° C, and even more preferably 40 to 50 ° C.
• a copolymer solution having a solid content concentration of 5 to 50% by mass is obtained, and a fluorine-containing copolymer can be obtained by removing the solvent from the copolymer solution.
• the fluorine-containing copolymer is separated from the copolymer solution by a method of evaporating and drying the copolymer solution, a method of adding a coagulant such as an inorganic salt to the copolymer solution to coagulate the fluorine-containing copolymer, and the like. Then, it is purified by a method of washing with a solvent or the like.
• the non-adhesive composition of the present invention can be obtained by mixing the fluorine-containing copolymer prepared as described above with a rubber component or a resin.
• the non-adhesive composition of the present invention may be obtained by mixing a rubber component or a raw material of a resin with a fluorine-containing copolymer and then performing treatments such as vulcanization and heating.
• DTFAC-103 (3,3,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl acrylate; single dose Body (a)) 1.7 g, StAc (stearyl acrylate; monomer (b)) 32.9 g, MEK (methyl ethyl ketone; solvent) 46.8 g, AIBN (azobisisobutyronitrile; polymerization initiator) 1.
• NDMC n-dodecyl mercaptan; chain mover
• the weight average molecular weight Mw of the obtained fluorine-containing copolymer 1 was measured by GPC and found to be 8200.
• Table 1 shows the blending amount of the raw materials, the recovered amount of the copolymer solution, the solid content concentration of the copolymer solution, and the weight average molecular weight of the fluorine-containing copolymer 1.
• Fluorine-containing copolymers 2 to 7 were prepared in the same manner as the fluorine-containing copolymer 1 except that the blending amount and type of the raw materials were changed as shown in Table 1.
• Table 1 shows the amount of the copolymer solution recovered when the fluoropolymers 2 to 7 were prepared, the solid content concentration of the copolymer solution, and the weight average molecular weight of the fluoropolymers 2 to 7.
• each symbol shown in Table 1 represents the following substances.
• DTFAC-103 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl acrylate (single amount) Body (a))
• DTFMAC-103 3,3,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl methacrylate (single dose) Body (a))
• StAc Stearyl acrylate (monomer (b))
• MEK Methyl ethyl ketone (solvent)
• AIBN Azobisisobutyronitrile (polymerization initiator)
• NDMC n-dodecyl mercaptan (chain transfer agent).
• Examples 1 to 7 and Comparative Examples 1 to 2 Each material was kneaded with an open roll at the blending amounts shown in Table 2 below to obtain a kneaded product.
• the obtained kneaded product was subjected to Mooney viscosity measurement, and the scorch time (t5) at 125 ° C. was measured according to ISO 289.
• press vulcanization primary vulcanization
• oven vulcanization secondary vulcanization
• the compression set at 200 ° C. for 70 hours was measured by a P-24 O-ring according to ASTM D395 and Method B.
• hardness, breaking strength, and breaking elongation were measured according to ISO 37 and ISO 7619-1 Type 1A. Table 2 shows the vulcanization conditions and the above measurement results.
• an evaluation test of releasability was conducted as follows. After putting the kneaded product in the O-ring mold of the release evaluation machine, primary vulcanization was performed at 205 ° C. for 3 minutes. The releasability of the crosslinked molded product when the crosslinked molded product after the primary vulcanization was taken out from the mold was visually evaluated according to the following criteria. ⁇ : There was no adhesion of the crosslinked molded product into the mold or damage to the crosslinked molded product, and the crosslinked molded product could be smoothly released from the mold.
• the non-adhesive composition of the present invention has excellent releasability.
• the composition of Comparative Example 1 did not contain the fluorine-containing copolymer of the present invention, and therefore had a releasability of "x".
• the composition of Comparative Example 2 contained a fluorine-based processing aid having a chemical structure different from that of the fluorine-containing copolymer of the present invention, the releasability was “ ⁇ ”.
• Example 8 100 parts by mass of polyurethane prepolymer heated to 80 ° C. (Coronate (registered trademark) C-4090 (trade name); manufactured by Nippon Polyurethane Industry Co., Ltd.), heat-melted methylenebis-o-chloroaniline curing agent (Iharacuamine) MT (trade name); manufactured by Kumiai Chemical Industry Co., Ltd.) 12.8 parts by mass and 1.0 part by mass of the fluorine-containing copolymer 1 prepared above are stirred and mixed while preventing bubbles from being involved to prepare a mixture. Obtained. The mixture was then injected into an aluminum mold (diameter 45 mm, depth 50 mm).
• a hook for taking out the cured molded product is set up in the center of the space of the mold, the mixture is heat-cured at 120 ° C. for 1 hour, and then the hook is pulled to obtain the molded product from the mold. I took it out. The release load at this time was 15 N.
• Example 8 The mixture obtained by stirring and mixing each material in the same manner as in Example 8 was applied to a stainless steel plate (2 ⁇ 5 cm), and then the mixture was heat-cured at 120 ° C. for 1 hour.
• the static contact angle and the dynamic contact angle (by the Cecil drop method), which are one index of the water and oil repellency, were measured for water and hexadecane.
• the measurement results of water repellency and oil repellency are shown below.
• Water repellency Water static contact angle 112 °, water fall angle (dynamic contact angle) 4 °
• Oil repellency Hexadecane static contact angle: 40 °, hexadecane fall angle (dynamic contact angle) 2 °.
• Example 8 the mixture of Comparative Example 3 was applied to a stainless steel plate (2 ⁇ 5 cm), and then the mixture was heat-cured at 120 ° C. for 1 hour.
• the static contact angle and the dynamic contact angle (by the Cecil drop method), which are one index of the water and oil repellency, were measured for water and hexadecane.
• the measurement results of water repellency and oil repellency are shown below.
• Example 8 From Example 8 and Comparative Example 3 above, it can be seen that the non-adhesive composition of the present invention has a low mold release load and excellent mold releasability. Further, in Example 8 as compared with Comparative Example 3, the static contact angle of water is large, the dynamic contact angle of water is small, the static contact angle of hexadecane is large, and the test piece of hexadecane at the time of measuring the dynamic contact angle No adhesion to the water was observed. Therefore, it can be seen that the molded product of the non-adhesive composition of the present invention is excellent in water and oil repellency.

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• 2020
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