CN102198714A - Film for demoulding - Google Patents

Film for demoulding Download PDF

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Publication number
CN102198714A
CN102198714A CN2011100356722A CN201110035672A CN102198714A CN 102198714 A CN102198714 A CN 102198714A CN 2011100356722 A CN2011100356722 A CN 2011100356722A CN 201110035672 A CN201110035672 A CN 201110035672A CN 102198714 A CN102198714 A CN 102198714A
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resin
film
compound
demoulding
mass parts
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CN2011100356722A
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CN102198714B (en
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大手道正
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Shin Etsu Polymer Co Ltd
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Shin Etsu Polymer Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
    • B29C33/64—Silicone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/68—Release sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0067—Using separating agents during or after moulding; Applying separating agents on preforms or articles, e.g. to prevent sticking to each other
    • B29C37/0075—Using separating agents during or after moulding; Applying separating agents on preforms or articles, e.g. to prevent sticking to each other using release sheets

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

The invention aims at providing a film for demoulding, which is advantaged by excellent stripping performance of forming products obtained by molding resin forming and processing with a molding mould, high strength of heat resistance, and no fusing of the film even under a use temperature of more than 200 DEG. A fluorosilicone compound layer is formed at least one surface of the film for demoulding. The film is obtained by forming of a resin composition comprising thermoplastic resin or forming of a resin composition with thermoplastic resin as the main component and a thermoplastic elastic body mixed. The fluorosilicone compound layer is obtained via coating and drying a demoulding composition on the film, wherein, the demoulding composition comprises a fluorosilicone compound provided with a monosilane group comprising a hydrolyzing part in a molecule.

Description

Demoulding film
Technical field
The present invention relates to demoulding film, this demoulding is used when resin moulded moulding or when making tellite or flexible printed circuit substrate etc. with film.
Background technology
For example semiconductor element such as transistor, IC (integrated circuit), LSI (large scale integrated circuit), super LSI or LED, optoisolator, phototransistor, photodiode, optical semiconductors such as CCD, CMOS are encapsulant with composition epoxy resin or organosilicon resin composition, and by based on the resin moulded moulding of transfer molding and sealed.
Use moulding-forming equipment in the above-mentioned semiconductor element or the sealing of optical semiconductor, will be injected in the molding die as moulding resin, carry out processing and forming by the encapsulant of composition epoxy resin or organosilicon resin composition.
As the method for the moulding product demoulding that molding die and processing and forming are obtained, for example, make the demoulding be practical (referring to patent documentation 1) with the method for film between molding die and moulding resin.The demoulding is supplied in the moulding-forming equipment with the mode of film with Roll toRoll (volume to volume), enter through temperature adjustment to the molding die of processing and forming temperature, through vacuum draw and with the molding die driving fit, fill moulding resin thereafter.Through certain hour post moulding resin solidification, open molding die this moment, and then the demoulding keeps aspirating state in molding die with film, and the moulding product are peeled off with film from the demoulding.This demoulding is used for example by the tetrafluoroethene-ethylene copolymer (ETFE resin) of thermoplastic fluorocarbon resin, the monofilm (referring to patent documentation 2) that hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) copolymer resins (FEP resin) forms at present with film.
But in the common resin moulded moulding about 180 ℃, the demoulding although it is so still surpasses in 200 ℃ the moulding in temperature with the fissility excellence of film and molding die and moulding product, the problem of film fusing can occur.
Need to prove that as the demoulding film that is formed by the thermoplastic resin except that the thermoplasticity fluororesin, the film that is formed by pet resin (PET resin), polymethylpentene resin (PMP resin) etc. is practicability.And, as the demoulding film that forms by the thermoplastic elastomer (TPE) except that the thermoplasticity fluororesin, the known method that the film that use forms by the resin combination that contains crystalline aromatic polyester is arranged, wherein, this crystalline aromatic polyester contains mutual-phenenyl two acid bromide two alcohol ester's (referring to patent documentation 3) in crystallised component.
Patent documentation 1: Japanese kokai publication hei 8-142105 communique
Patent documentation 2: TOHKEMY 2001-310336 communique
Patent documentation 3: TOHKEMY 2007-224311 communique
Summary of the invention
But, as demoulding film, shown in patent documentation 3, when using by pet resin (PET resin), polymethylpentene resin (PMP resin) or containing the film that the resin combination of the crystalline aromatic polyester that comprises the mutual-phenenyl two acid bromide two alcohol ester in crystallised component forms, in the general resin moulded moulding in about 180 ℃, can appearance and the not enough such problem of fissility of molding die or moulding product.So, actual conditions are that in resin moulded moulding, the film that is formed by composition except that the thermoplasticity fluororesin can't be used as demoulding film suitably.
The present invention is in view of above-mentioned actual conditions, its purpose is to provide a kind of demoulding film, itself and molding die and with the fissility excellence of the resulting moulding product of moulding resin processing and forming, and have high-temperature capability concurrently, even surpassing under 200 ℃ the serviceability temperature, film can not fuse yet.
In order to solve above-mentioned problem, the demoulding of the present invention is characterised in that with film, to comprise the resin combination moulding of thermoplastic resin or will and be mixed with the resin combination moulding of thermoplastic elastomer (TPE) and obtain film based on thermoplastic resin, one side at least at resulting film is coated with mold release compositions and carries out drying, form the fluorosilicone compound layer, described mold release compositions contains the fluorosilicone compound that has the silicyl that contains water-disintegrable position in molecule.
And, foregoing invention is characterised in that thermoplastic resin is polyphenylene sulfide (a PPS resin), polysulfone resin (PSF resin), polyethersulfone resin (PES resin), polyether-ether-ketone resin (PEEK resin), polyimide resin (PI resin), polyamide-imide resin (PAI resin), polyetherimide resin (PEI resin), PEN resin (PEN resin), polyamide (PA resin), polyacetal resin (POM resin), polycarbonate resin (PC resin), polyphenylene oxide resin (PPE resin), polybutylene terephthalate (PBT) resin (PBT resin), pet resin (PET resin), cyclic polyolefin resin (COP resin), syndiotactic polytyrene resin (SPS resin), polymethylpentene resin (PMP resin), plexiglass (PMMA resin), polyvinyl resin (PE resin), acrylic resin (PP resin), polystyrene resin (PS resin), vinylite (PVAc resin), at least a resin among acrylonitrile butadiene styrene resin (ABS resin) and the AS resin acrylonitrile styrene resin (AS resin); Thermoplastic elastomer (TPE) is at least a elastomer among polyester based elastomers (shorthand notation is TPEE), polyamide-based elastomer (shorthand notation is TPA), polyurethane series elastomer (shorthand notation is TPU), styrene series elastomer (shorthand notation is TPS) and the olefin-based elastomer (shorthand notation is TPO).
And, foregoing invention is characterised in that, mold release compositions has the fluorosilicone compound of the silicyl that contains water-disintegrable position with respect to 100 mass parts in molecule, contain a kind of compound or the two or more compound that is selected from the group of being made up of organic titanic compound, organic zirconate and organo-silicon compound with the scope of 0.05 mass parts～20 mass parts.
And, foregoing invention is characterised in that, mold release compositions has the fluorosilicone compound of the silicyl that contains water-disintegrable position with respect to 100 mass parts in molecule, contain a kind of compound or the two or more compound that is selected from the group of being made up of organic titanic compound and organic zirconate with the scope of 0.05 mass parts～20 mass parts.
And, foregoing invention is characterised in that, mold release compositions has the fluorosilicone compound of the silicyl that contains water-disintegrable position in molecule with respect to 100 mass parts, scope with 0.05 mass parts～20 mass parts contains a kind of compound or the two or more compound that is selected from the group of being made up of organic titanic compound and organic zirconate, and contains organo-silicon compound with the scope of 0.05 mass parts～20 mass parts.
And, the invention is characterized in, will comprise the resin combination moulding of thermoplastic resin or will obtain based on thermoplastic resin and the resin combination moulding that is mixed with thermoplastic elastomer (TPE), the thickness of monofilm or two-layer above multilayer film is the scope of 5 μ m～500 μ m; By coating mold release compositions and the thickness that carries out the fluorosilicone compound layer that drying obtains is the scope of 0.05 μ m～10 μ m, and described mold release compositions contains the fluorosilicone compound that has the silicyl that contains water-disintegrable position in molecule.
According to demoulding film of the present invention, itself and molding die and with the fissility excellence of the resulting moulding product of moulding resin processing and forming can have the corresponding high-temperature capability that surpasses 200 ℃ serviceability temperature simultaneously concurrently.
Description of drawings
Fig. 1 is the sectional view of the expression demoulding of the present invention with an embodiment of film.
Fig. 2 makes the signal pie graph of the demoulding of the present invention with an embodiment of the film manufacturing device of film for expression.
Fig. 3 is the sectional view of the periphery of the cast hopper of expression film manufacturing device shown in Figure 2.
Symbol description
1 extruder
2 cast hoppers
3 nitrogen are supplied with pipe
4 tube connectors
5 filters
6 gear pumps
7 T-die heads
The 7a die lip
8 films
9 crimping rollers
10 chill rolls
11 hauling machines
12,13 transmit pair roller
14 thickness testers
16 batch pipe
20 films
30 mold release compositions
The specific embodiment
The inventor in order to achieve the above object, various researchs have been carried out, found that, to comprise the resin combination moulding of thermoplastic resin, perhaps will and be mixed with the resin combination moulding of thermoplastic elastomer (TPE) and obtain film based on thermoplastic resin, one side at least at resulting film is coated with mold release compositions (this mold release compositions contains the fluorosilicone compound that has the silicyl that contains water-disintegrable position in molecule) and carries out drying, when forming the fluorosilicone compound layer, then can obtain with molding die with the fissility excellence of the resulting moulding product of moulding resin processing and forming, and have the corresponding demoulding film of high-temperature capability that surpasses 200 ℃ serviceability temperature concurrently.
After further study, found that, by making mold release compositions in molecule, have the fluorosilicone compound of the silicyl that contains water-disintegrable position with respect to 100 mass parts, when containing a kind of compound that is selected from the group of being made up of organic titanic compound, organic zirconate and organo-silicon compound or two or more compound with the scope of 0.05 mass parts～20 mass parts altogether, effect is better.
Herein, as thermoplastic resin, can use for example polyphenylene sulfide, polysulfone resin, polyethersulfone resin, polyether-ether-ketone resin, polyimide resin, polyamide-imide resin, polyetherimide resin, the PEN resin, polyamide, polyacetal resin, polycarbonate resin, polyphenylene oxide resin, the polybutylene terephthalate (PBT) resin, pet resin, cyclic polyolefin resin, the syndiotactic polytyrene resin, the polymethylpentene resin, plexiglass, polyvinyl resin, acrylic resin, polystyrene resin, vinylite, at least a in acrylonitrile butadiene styrene resin and the AS resin acrylonitrile styrene resin.
And,, can use at least a in for example polyester based elastomers, polyamide-based elastomer, polyurethane series elastomer, styrene series elastomer and the olefin-based elastomer as thermoplastic elastomer (TPE).
These thermoplastic resins and thermoplastic elastomer (TPE) can be selected aptly to use according to desired high-temperature capability.As preferred thermoplastic resin, polyphenylene sulfide, polysulfone resin, polyethersulfone resin, polyether-ether-ketone resin, polyimide resin, polyamide-imide resin, polyetherimide resin, PEN resin, polyamide, polyacetal resin, polycarbonate resin, polyphenylene oxide resin, polybutylene terephthalate (PBT) resin, pet resin, cyclic polyolefin resin, syndiotactic polytyrene resin and polymethylpentene resin are for example arranged.In addition, as preferred thermoplastic resin, polyphenylene sulfide, polysulfone resin, polyethersulfone resin, polyether-ether-ketone resin, polyimide resin, polyamide-imide resin, polyetherimide resin, PEN resin, cyclic polyolefin resin, syndiotactic polytyrene resin and polymethylpentene resin are for example arranged.And,, polyester based elastomers, polyamide-based elastomer, styrene series elastomer and olefin-based elastomer are for example arranged as preferred thermoplastic elastomer (TPE).In addition, as preferred thermoplastic elastomer (TPE), polyester based elastomers, polyamide-based elastomer and styrene series elastomer are arranged.
Among the present invention,, can enumerate polyetherimide resin as the amorphism thermoplastic resin as the resin combination that comprises thermoplastic resin.And as being principal component and the resin combination that is mixed with thermoplastic elastomer (TPE) with the thermoplastic resin, can enumerate with the syndiotactic polytyrene resin as the crystalline thermoplastic resin is principal component and the resin combination that is mixed with styrene series elastomer.But the present invention is not limited to these resin combinations.
Polyetherimide resin for example is the resin of following chemical formula (1) or (2) expression.Need to prove that chemical formula (1) or (2) are represented with the form of resin with repetitive.
Figure BDA0000046567180000051
Figure BDA0000046567180000061
For this polyetherimide resin, specifically, (SABIC Innovative Plastics Japan company makes can to enumerate glass transition temperature and be 211 ℃ Ultem1000-1000, trade name), glass transition temperature is 223 ℃ Ultem 1010-1000 (SABIC Innovative Plastics Japan company manufacturing, trade name), glass transition temperature is 235 ℃ Ultem CRS5001-1000 (SABIC Innovative Plastics Japan company makes, trade name) etc.
Need to prove,, but can also use block copolymer, random copolymer or the modifier that forms with the monomer of other copolymerization as polyetherimide resin.For example, can use glass transition temperature as polyetherimide sulfone copolymer is 252 ℃ Ultem XH6050-1000 (SABIC Innovative Plastics Japan company makes, trade name).And polyetherimide resin can be used alone, and perhaps can also or mix and use two or more alloyings.
Above-mentioned syndiotactic polytyrene resin is the crystalline thermoplastic resin, and its stereochemical structure is different with general polystyrene resin, and stereoregularity has syndiotactic structure.More particularly, have the side chain phenyl and alternately be positioned at rightabout stereochemical structure with respect to the main chain that forms by carbon-carbon bond.Therefore stereoregularity height with syndiotactic polytyrene resin of such structure becomes the polystyrene resin of crystallization.
For the syndiotactic polytyrene resin, it is 270 ℃ XAREC C102 (Idemitsu Kosen Co., Ltd. make, trade name) that concrete example can be enumerated fusing point.And,, can be the polymer alloy that forms with general polystyrene resin as suitable syndiotactic polytyrene resin of the present invention.
Similarly, also can be mixed with styrene series elastomer in the syndiotactic polytyrene resin to give flexibility.As styrene series elastomer, can enumerate hydrogenated derivatives (shorthand notation is SEBS), the styrene-isoprene-phenylethene triblock copolymer (shorthand notation is SIPS) of for example s-B-S triblock copolymer (shorthand notation is SBS), s-B-S triblock copolymer, hydrogenated derivatives (shorthand notation is SEPS) of styrene-isoprene-phenylethene triblock copolymer etc.
For this styrene series elastomer, specifically, can enumerate KRATON G-1657 (Kraton Polymers company makes, trade name), it is that styrene-content is the hydrogenated derivatives of the s-B-S triblock copolymer of 13 quality %.
Need to prove, above-mentioned film can be in the scope that keeps high-temperature capability aptly by individual layer or two-layer more than multilayer film constitute.
The demoulding used in the present invention contains the fluorosilicone compound that has the silicyl that contains water-disintegrable position in molecule with composition.In addition, for such fluorosilicone compound all cpds has been proposed.These fluorosilicone compounds are coated mould usually and are used.But, the invention is characterized in, these fluorosilicone compounds are coated the surface of film, form the fluorosilicone compound layer.Fig. 1 is the sectional view of the expression demoulding that constitutes like this with an embodiment of film.Among the figure, symbol 20 expression films, symbol 30 expression mold release compositions.Herein, film 20 can be monofilm or two-layer above multilayer film.In addition, mold release compositions 30 also can be formed on the another side of film 20, can also be formed on the two sides.
As above-mentioned fluorosilicone compound (in molecule, having the silicyl that contains water-disintegrable position), for example, can enumerate the compound of following chemical formula (3) expression.
Figure BDA0000046567180000071
In the formula of chemical formula (3), R 1～R 10Can be preferred C 1-20(more preferably C 1-20) replacement or the alkyl or the C of non-replacement 6-20(C more preferably 6-12) replacement or the aryl of non-replacement.Abovementioned alkyl can have halogen atom substituting groups such as chlorine replacing group.And above-mentioned aryl also can have halogen atom substituting groups such as chlorine replacing group, perhaps can have for example C such as methyl 1-10Alkyl substituent.R 1～R 10Comprise for example non-substituted alkyls such as methyl, ethyl, propyl group, hexyl and dodecyl; Substituted alkyls such as chloromethyl; Non-substituted aryl such as phenyl and naphthyl; Substituted aryls such as 4-chlorphenyl and 2-aminomethyl phenyl.Among these groups, preferred alkyl, preferred especially non-substituted alkyl, more preferably methyl.
R 3And R 10Can be Rf-X-or Z-Y-.Herein, X and Y are identical or different respectively divalent organic groups, and Rf is C 1-6Fluoro-alkyl, Z is the silicyl that contains water-disintegrable position.
X and Y are preferably C 1-20Divalent organic group, C more preferably 1-12The divalent organic group.The example of divalent organic group is preferably C 1-12Alkylidene (for example ethylidene, propylidene, methyl ethylidene, Ya Xinji and inferior decyl); And preferred C 2-12Alkylidene oxygen base alkylidene (for example ethyleneoxy group methylene, propylidene oxygen methylene, propylidene oxygen base ethylidene and ethyleneoxy group butylidene).In addition, X is preferably C 1-12Alkylidene amide groups (for example ethylidene amide groups, propylidene amide groups and inferior decyl amide groups etc.).Preferred X and Y are-(CH 2) r-.Herein, in the formula, r is 2～200, is in particular 2～12.
Rf is a fluoro-alkyl, is preferably perfluoroalkyl, and Rf contains 1～6 carbon atom, for example contains 1～5 carbon atom, particularly 1～4 carbon atom.Specifically, Rf is trifluoromethyl, pentafluoroethyl group, 1,1,2,2-tetrafluoro ethyl, 2-trifluoromethyl-perfluor ethyl, perfluoro butyl, perfluor amyl group and perfluoro hexyl.Among these groups, preferred pentafluoroethyl group.
Z is for for example having the silicyl that contains water-disintegrable position of 1～60 carbon atom.Z can be-Si (R 11) q(X ') 3-q(R 11For alkyl with 1～20 carbon atom, be preferably alkyl with 1～4 carbon atom, X ' is water-disintegrable position, q is 0,1 or 2.)。And, Z can for
-(Si(R 11) 2O) r-Si(R 11) q(X’) 3
(R 11Be that carbon number is that 1～20 alkyl, preferred carbon number are 1～4 alkyl, X ' is water-disintegrable position, and r is 1～200).R 11Can most preferably be methyl for methyl, ethyl, propyl group, hexyl or dodecyl.As the X ' at water-disintegrable position, for example comprise halogens such as chlorine and bromine; Methoxyl group, ethyoxyl, propoxyl group, methoxyethoxy and butoxy etc. preferably have the alkoxyl of 1～12 carbon atom; Acetoxyl group, propionyloxy and benzoyloxy etc. preferably have the acyloxy of 1～12 carbon atom; Alkenyl oxies such as isopropenyl oxygen base and isobutenyl oxygen base; Dimethyl ketone oximido, methyl ethyl ketone oximido, metacetone oximido and cyclohexanone oximido etc. preferably have the imino group oximido (imino-oxime) of 1～12 carbon atom; Ethylamino, diethylamino and dimethylamino etc. preferably have the substituted-amino of 1～12 carbon atom and at least 1 alkyl substituent; N-methylacetamide base and N-ethyl acetamide base etc. preferably have the amide groups of 1～12 carbon atom; Diformazan azyloxy and diethyl azyloxy etc. preferably have 1～12 carbon atom and have at least 1 replacement azyloxy that preferably has the alkyl substituent of 1～4 carbon atom.
At this, the m of above-mentioned formula (3) is 1～100, n is 1～50, o is 0～200.Preferred m is 1～50, n is 3～20, o is 0～100.Make more preferably that m is 2～50, n is 3～20, o is 1～100.
As the concrete example of above-claimed cpd, can enumerate compound with chemical formula (4) expression, in this compound, A is-(CH 2) 3OCH 2CF 2CF 3Perhaps-(CH 2) 3OCH 2CH 2CF 2CF 2CF 2CF 3, B is-(CH 2) 3Si (OCH 3) 3
Figure BDA0000046567180000091
Herein, in the formula, Me is a methyl.X is 1～100, y is 1～50, z is 0～200.
And above-mentioned fluorosilicone compound (having the silicyl that contains water-disintegrable position in molecule) can be the compound with chemical formula (5) expression.
Figure BDA0000046567180000092
The compound of chemical formula (5) in 1 molecule, have respectively be more than 1 and silicon atom bonding main chain, with general formula :-R 1-SiR 2 (3-m)X mThe expression the silicyl alkylidene and with general formula :-R 1C nF (2n+1)The fluorine-containing organic group of expression.In the following formula, R 1Be alkylidene or alkylidene oxygen base alkylidene, as alkylidene, for example can enumerate ethylidene, methyl ethylidene, ethyl ethylidene, propyl group ethylidene, butyl ethylidene, propylidene, butylidene, 1-methyl propylidene, pentylidene, hexylidene, inferior heptyl, Ya Xinji, inferior nonyl, inferior decyl; As alkylidene oxygen base alkylidene, for example can enumerate the ethyleneoxy group ethylidene, ethyleneoxy group propylidene, ethyleneoxy group butylidene, propylidene oxygen base ethylidene, propylidene oxygen base propylidene, propylidene oxygen base butylidene, butylene oxide base ethylidene, butylene oxide base propylidene.R 2Be identical or different being selected from by alkyl, aryl and 3,3, group in the group that the 3-trifluoro propyl is formed as alkyl, for example can be enumerated methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, cetyl, octadecyl; As aryl, for example can enumerate phenyl, tolyl, xylyl.X is halogen atom or alkoxyl, as halogen atom, for example can enumerate fluorine atom, chlorine atom, bromine atoms; As alkoxyl, for example can enumerate methoxyl group, ethyoxyl, propoxyl group, butoxy, methoxy ethoxy.Herein, m is 1～3 integer.N is the integer more than 4, preferred 4～12 integer.As the fluorine-containing organic group of representing with following formula, can enumerate for example nine fluorine hexyls, ten trifluoro iso-octyl, ten trifluoro octyl groups, 17 fluorine decyls, nine fluorine butyl ethoxyethyl groups, nine fluorine butyl ethoxycarbonyl propyls, nine fluorine butyl ethyoxyl butyl, 11 fluorine amyl group ethoxyethyl groups, 11 fluorine amyl group ethoxycarbonyl propyls.The silicyl alkylidene of representing with following formula and the bonding position of fluorine-containing organic group can be molecule chain end, also can be side chain, can also for molecule chain end and side chain the two.As the group that is bonded to silicon atom except that these groups, for example can enumerate the monovalence alkyl, specifically, can enumerate illustrative group with above-mentioned R2.The organopolysiloxane that constitutes main chain is preferably the straight chain shape, but also can a part be a chain, ring-type, netted.This organopolysiloxane preferably is liquid at normal temperatures, and 25 ℃ preferred viscosities is 5～100,000 centistoke's Si a scope.As this composition, can use a kind of above-mentioned organopolysiloxane, it is two or more also can to mix use.
In the formula, R 3Be identical or different being selected from, 3-trifluoro propyl and with general formula :-R by alkyl, aryl, 3,3 1C nF (2n+1)Group in the group that the fluorine-containing organic group of expression is formed, wherein, at least 1 R 3Be the fluorine-containing organic group of representing with following formula.As alkyl, aryl and fluorine-containing organic group, can enumerate the group same with above-mentioned group.R 1, R 2, X, m and n be same as described above.Herein, d is 1～10,000 integer, is preferably 1～1,000 integer.And e is 1～1,000 integer, is preferably 1～100 integer.
Among the present invention, among the above-mentioned fluorosilicone compound (having the silicyl that contains water-disintegrable position in molecule), the compound of representing with chemical formula (4) is to be fit to use.
The mold release compositions of using among the present invention must contain the fluorosilicone compound that has the silicyl that contains water-disintegrable position in molecule.This be because, as mold release compositions, suppose to use under the situation of fluorosilicone compound of the silicyl that does not contain water-disintegrable position in the molecule, when using film as the demoulding, if the moulding product are peeled off with film by the demoulding, then mold release compositions is also moved to the surface of moulding product by the film sur-face peeling, thereby produces the problem of polluting the moulding product.With respect to this, use has in molecule under the situation of fluorosilicone compound of the silicyl that contains water-disintegrable position, owing to the surface-crosslinked chemical bond that forms of film, therefore mold release compositions pollutes the problem on the surface of moulding product by the film sur-face peeling in the time of can avoiding using.Need to prove that the fluorosilicone compound that has the silicyl that contains water-disintegrable position in molecule of the present invention is not limited in above-claimed cpd, for example, can enumerate compound with chemical formula (6) and chemical formula (7) expression.
F-(CF 2) q-(OC 3F 6) m-(OC 2F 4) n-(OCF 2) o(CH 2) pX(CH 2) rSi(X’) 3-a(R 1) a
......(6)
Herein, in the formula (6), q is 1～3 integer.M, n and o are respectively 0～200 integer.P is 1 or 2.X is oxygen or divalent organic group.R is 2～20 integer.R 1Be C 1-22The alkyl of straight or branched.A is 0～2 integer.X ' is a hydrolization group.And when a was 0 or 1, z was 0～10 integer.
F-(CF 2) q-(OC 3F 6) m-(OC 2F 4) n-(OCF 2) o(CH 2) pXX”Si(X’) 3-a(R 1) a
......(7)
Herein, in the formula (7), q is 1～3 integer.M, n and 0 are respectively 0～200 integer.P is 0,1 or 2.X is oxygen or divalent organic group.X " be divalence organic silicone group at interval.X ' is a hydrolization group.And when a was 0 or 1, z was 0～10 integer.
Preferred above-mentioned fluorosilicone compound (having the silicyl that contains water-disintegrable position in molecule) is dissolved in organic solvent etc. and uses with the form of solution.As the concrete example of solvent, can enumerate sturated aliphatic hydrocarbon kind solvents such as hexane, isohexane, heptane, octane and isooctane; Aliphatic series solvents such as cyclohexane, hexahydrotoluene and dimethyl cyclohexane; Aromatic series series solvents such as benzene, toluene and dimethylbenzene; Ester such as ethyl acetate and butyl acetate series solvent; Pure series solvent such as ethanol and isopropyl alcohol; Chlorine series solvents such as trichloro-ethylene, chloroform and chlordene meta-xylene; Ketones solvents such as acetone, methyl ethyl ketone and methyl iso-butyl ketone (MIBK); Ether series solvents such as diethyl ether, diisopropyl ether and oxolane; Fluorine kind solvents such as methyl perfluor butyl ether and ethyl perfluor butyl ether; Silicone-based solvents such as HMDO, hexamethyl cyclotrisiloxane and seven methyl trisiloxanes etc.
Above-mentioned mold release compositions can also contain organic titanic compound, organic zirconate and organo-silicon compound.These compounds play the effect of the crosslinking agent between film surface and the fluorosilicone compound (having the silicyl that contains water-disintegrable position in molecule) and the effect of fluorosilicone compound crosslinking and curing agent each other.And these compounds can use a kind of or be used in combination two or more.
For organic titanic compound, can enumerate for example two (ethyl acetoacetate) metatitanic acid diisopropyl ester (Ti (OiC herein, 3H 7) 2(C 6H 9O 3) 2), two octyloxies two (ethohexadiol) close titanium (Ti (OC 8H 17) 2(C 8H 17O 2) 2, チ タ Application ジ オ Network チ ロ キ シ PVC ス (オ Network チ レ Application グ リ コ レ one ト)), four acetyl acetone titaniums and diisopropoxy two (acetylacetone,2,4-pentanedione) close titanium chelate classes such as titanium; Alkoxytitanium classes such as four-2-Ethylhexyl Alcohol titanium, titanium butoxide dimer, four titanium n-butoxide and tetraisopropoxy titanium, stability, crosslinking rate and the crosslinking curing speed that can consider compound itself wait to be selected to use aptly.Among these, preferred usually two (ethyl acetoacetate) metatitanic acid diisopropyl esters, four-2-Ethylhexyl Alcohol titanium and the tetraisopropoxy titanium etc. of using.
And,, for example can enumerate four acetyl acetone zirconiums, two (ethyl acetoacetate) zirconic acid dibutyl ester (Zr (OnC for organic zirconate 4H 9) 2(C 6H 9O 3) 2, ジ Le コ ニ ウ system ジ Block ト キ シ PVC ス (エ チ Le ア セ ト ア セ テ one ト)), single butoxy (acetylacetone,2,4-pentanedione) two (ethyl acetoacetate) zirconium (Zr (OnC 4H 9) (C 5H 7O 2) (C 6H 9O 3) 2, ジ Le コ ニ ウ system モ ノ Block ト キ シ ア セ チ Le ア セ ト ネ one ト PVC ス (エ チ Le ア セ ト ア セ テ one ト)), three butoxy single acetyl acetone close zirconium chelate classes such as zirconium and four acetyl acetone zirconiums; Zirconium alkoxide classes such as four n-butoxy zirconiums and four n-propoxyzirconium, stability, crosslinking rate and the crosslinking curing speed that can consider compound itself wait to be selected to use aptly.
Above-mentioned organic titanic compound and organic zirconate are mainly brought into play the effect as the crosslinking agent between film surface and the fluorosilicone compound.With respect to 100 mass parts fluorosilicone compounds, its addition is that the scope of 0.05 mass parts～20 mass parts, the scope that is preferably 0.1 mass parts～10 mass parts get final product.In this case, if addition less than 0.05 mass parts, the crosslinked deficiency between film surface and the fluorosilicone compound then, so not preferred.And, if add to surpass 20 mass parts, crosslinked abundant between film surface and the fluorosilicone compound then, and unreacted organic titanic compound or organic zirconate or the two may be remaining, so not preferred.
Organo-silicon compound generally can use the compound that is called as silane coupling agent.As organo-silicon compound, for example can enumerate 3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-(2-amino-ethyl) TSL 8330,3-(2-amino-ethyl) aminopropyltriethoxywerene werene, 3-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) propylamine, 3-phenyl amino propyl trimethoxy silicane and N-(to vinyl benzyl)-N-(trimethoxy-silylpropyl) ethylenediamine etc. and contain amino silane coupling agent; 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-glycidoxy propyl group methyldiethoxysilane and 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc. contain the silane coupling agent of epoxy radicals; Vinyltrimethoxy silane, VTES, vinyl silane triisopropoxide, vinyltriacetoxy silane and vinyl trichlorosilane etc. contain the silane coupling agent of vinyl; 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl triethoxysilane and 3-methacryloxypropyl methyldiethoxysilane etc. contain the silane coupling agent of methacryl; 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl group methyl dimethoxysilane, 3-sulfydryl propyl-triethoxysilicane and 3-sulfydryl propyl group methyldiethoxysilane etc. contain the silane coupling agent of sulfydryl; Allyltrimethoxysilanis and diallyl dimethylsilane etc. contain allylic silane coupling agent; Two (3-(triethoxysilyl) propyl group) disulphide and two (3-(triethoxysilyl) propyl group) tetrasulfide etc. contain the silane coupling agent of sulfenyl.Among these compounds, preferably contain amino silane coupling agent, the silane coupling agent that contains epoxy radicals, more preferably 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-(2-amino-ethyl) TSL 8330,3-(2-amino-ethyl) aminopropyltriethoxywerene werene, 3-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-glycidoxy propyl-triethoxysilicane and 3-glycidoxy propyl group methyldiethoxysilane, further preferred 3-TSL 8330 and 3-aminopropyltriethoxywerene werene.
Organo-silicon compound are mainly brought into play the effect as the crosslinking and curing agent between the fluorosilicone compound (having the silicyl that contains water-disintegrable position in molecule).With respect to 100 mass parts fluorosilicone compounds (having the silicyl that contains water-disintegrable position in molecule), its addition is that the scope of 0.1 mass parts～20 mass parts, the scope that is preferably 0.05 mass parts～10 mass parts get final product.In this case, if addition less than 0.05 mass parts, the curing deficiency of fluorosilicone compound (in molecule, having the silicyl that contains water-disintegrable position) then, therefore not preferred.And, surpassing 20 mass parts even add, the crosslinking curing of fluorosilicone compound (having the silicyl that contains water-disintegrable position in molecule) is also abundant, and unreacted organo-silicon compound may be remaining, and are therefore not preferred.
Mold release compositions of the present invention preferably will be selected from a kind of compound in the group of being made up of organic titanic compound and organic zirconate or two or more compound and organo-silicon compound and share.Organic titanic compound and organic zirconate mainly promote crosslinked between film surface and the fluorosilicone compound, and organo-silicon compound mainly promote the crosslinking curing of fluorosilicone compound.Therefore, by share them, under the state of film surface and fluorosilicone compound crosslink, the fluorosilicone compound is cross-linked to each other, and forms network structure.Thus, when using film, even film is stretched as the demoulding, comprise filming yet of fluorosilicone compound, and filming is not destroyed and is kept along with film extends, therefore can keep fissility, and the fluorosilicone compound that forms after filming can not move to the moulding product to moulding resin.In addition, in the fabrication stage, also can obtain to shorten such subsidiary effect drying time after the coating.
Above-mentionedly comprise the resin combination of thermoplastic resin or be that principal component and the film that is mixed with the resin combination of thermoplastic elastomer (TPE) (below, be sometimes referred to as matrix membrane) can come moulding by existing known method such as for example extrusion by melting or fusion-cast methods with the thermoplastic resin.
In the following example, enumerate extrusion by melting by using the T-die head with the method for matrix membrane moulding.
The matrix membrane that utilizes such method to obtain obtains in the following way: use extruders such as single screw extrusion machine or double screw extruder, characteristic according to resin combination, under the atmosphere after the air displacement that will be present in the gap in the extruder and between moulding material with nitrogen, the moulding material that to the resin combination that comprises thermoplastic resin or with the thermoplastic resin is principal component and the resin combination that is mixed with thermoplastic elastomer (TPE) carries out melting mixing, die lip by the T-die head front end that is disposed at the extruder front end melt extrudes matrix membrane, this matrix membrane is clipped between crimping roller in the hauling machine and the chill roll cools off, next batch successively in batching on the pipe with coiling machine, thereby obtain matrix membrane.
Fig. 2 is that expression utilizes above-mentioned method to make the schematic pie graph of the film manufacturing device of matrix membrane.And Fig. 3 is the sectional view of periphery of the cast hopper of film manufacturing device shown in Figure 2.Among Fig. 2, film manufacturing device roughly possesses cast hopper 2, extruder 1, T-die head 7, hauling machine 11, coiling machine 15 and constitutes.Cast hopper 2 is used to drop into moulding material, as shown in Figure 3, links to each other midway with extruder 1 at cast hopper 2, and nitrogen is supplied with managing 3 and inserted via distance piece 3a.And nitrogen is supplied with the pipe 3 approximate centre bending shafts along material input port 1c, and its front end extends near the periphery that is set to the extrusion screw rod 1a in the extruder 1.When mixing with the extrusion screw rod 1a of extruder 1, when stirring moulding material, using and supply with in the moulding material that the nitrogen replacements supplied with pipe 3 drop into by cast hopper 2 or the extruder 1 interior oxygen that is contained by nitrogen.
When extruder 1 utilizes extrusion screw rod 1a to be mixed into the section bar material, transmit moulding material along the arrow B direction, by the electric calorifie installation in the machine barrel 1b that is assembled into extruder 1 with moulding material heating, fusion.So, the moulding material that is melted and is transmitted is sent to filter element 5 by tube connector 4 shown in Figure 2.Then, utilize filter element 5,, the moulding material after the fusion is delivered to gear pump 6 the moulding material separation of not fusion.Gear pump 6 improves the pressure of the moulding material after the fusion, extrudes the melt molding material to T-die head 7 simultaneously.T-die head 7 is extruded the melt molding material with predetermined pressure, is molded the film 8 of predetermined thickness, preset width by the die lip 7a of T-die head 7.The film 8 of moulding is towed on the outer peripheral face of chill roll 10 of hauling machine 11 on one side like this, with crimping roller 9 is adjusted to predetermined thickness on one side, and then cooling, solidify, and is sent to coiling machine 15 with transmission pair roller 12,13.
In the coiling machine 15, film 8 is guided by guide reel 15a, 15b, 15c, and is batched pipe 16 and batch.Need to prove, between transmission pair roller 12,13 and guide reel 15a, be equipped with thickness tester 14,, the peripheral speed degree of chill roll 10 is adjusted, controlled, to reach desirable thickness based on the thickness that utilizes thickness tester 14 to measure.So form above-mentioned matrix membrane.
The surface configuration of matrix membrane and moulding product forms surface configuration accordingly.For example, IC or LSI etc. are formed with micro concavo-convex on its surface, therefore use the demoulding film that has formed micro concavo-convex on the surface of matrix membrane.And, be under the situation of minute surface in its surfaces such as LED, use the demoulding film of the surface of matrix membrane being made minute surface.
Method as the surface configuration that forms matrix membrane, be formed with in the situation of micro concavo-convex on the surface, following method is comparatively easy: the outer peripheral face at above-mentioned metal chill roll forms micro concavo-convex in advance, when the matrix membrane that utilizes crimping roller will be in molten condition is crimped on this chill roll, make the micro concavo-convex that is formed at the chill roll outer peripheral face be transferred to the matrix membrane surface.And, the surface to be made in the situation of minute surface, following method is comparatively easy: in advance minute surface is made on the surface of above-mentioned metal chill roll, the matrix membrane that utilizes crimping roller will be in molten condition is crimped on this chill roll, is minute surface with the surfacing of matrix membrane.
Thereafter, the one side at least at matrix membrane is coated with mold release compositions and carries out drying, formation fluorosilicone compound layer.The coating of mold release compositions can be used existing known coating method.For example, can be coated with that machine, Kohler coater, knife type coater, bar are coated with machine, cutter is coated with and selects aptly machine, extrusion coating machine, the dip coaterd etc. to use from scraping strip coating machine, reverse roll coater, positive rotation roll-coater, intaglio plate coating machine, kiss-coating machine, casting coating machine, flush coater, curtain coater, mould.
For the demoulding of the present invention for film, the thickness of matrix membrane be 5 μ m～500 μ m scope, be preferably the scope of 10 μ m～400 μ m, get final product according to suitable selection of shape of employed molding die.When the thickness of matrix membrane during less than 5 μ m, exist when using because of the damaged problem of the pressure of moulding resin, therefore not preferred.And, when surpassing 500 μ m, exist to hinder the heat conduction, produce indenture etc. on the surface of moulding product and the problem that causes yields to descend, thus not preferred.And, the thickness of fluorosilicone compound layer be 0.05 μ m～10 μ m scope, be preferably the scope of 0.1 μ m～5 μ m.When the thickness of fluorosilicone compound layer during less than 0.05 μ m, have that the pressure because of moulding resin causes the fluorosilicone compound layer destroyed when using, thereby lose the problem of fissility, therefore not preferred.And, when surpassing 10 μ m, can't expect that fissility further improves, and the drying after the coating needs the long period, thereby productivity ratio reduces, therefore not preferred.In addition, because the flexibility of fluorosilicone compound layer itself, the problem that exists the planar portions of moulding product to expand, so not preferred.
Embodiment
Below, using table 1 and table 2, the embodiment 1～embodiment 10 with film describes to the demoulding of the present invention.
In the table 1, each content of embodiment 1～embodiment 5 is shown laterally; In the table 2, each content of embodiment 6～embodiment 10 is shown laterally.And in each table of table 1 and table 2, vertically classification illustrates matrix, mold release compositions, the demoulding and estimates with film successively.Classification illustrates resin combination, matrix membrane thickness in the item of matrix, and classification illustrates composition, wet coating thickness, dry back thickness in the item of mold release compositions.In addition, classification illustrates solid constituent (mass parts), organic titanic compound (mass parts), organic zirconate (mass parts), organo-silicon compound (mass parts) in the item of forming.In the item of the demoulding, classify fissility, high-temperature capability are shown with the film evaluation.And, in the item of fissility classification illustrate dry 2 minutes, dry 5 minutes, dry 10 minutes, dry 15 minutes, at each vertical, horizontal shown in the item of high-temperature capability E ' (Pa).Need to prove that the demoulding that the present invention is correlated with is not subjected to embodiment 1～embodiment 10 any qualifications with film.
Herein, the resin combination shown in table 1 and the table 21, resin combination 2, fluorosilicone compound, organic titanic compound, organic zirconate, organo-silicon compound have used material as follows.Need to prove that table 3 and table 4 are to illustrate simultaneously and corresponding comparative example of embodiments of the invention (comparative example 1～comparative example 7) and the table estimated thereof.Therefore, the content that in the situation of comparative example, illustrates below the application similarly.
(resin combination 1; Thermoplastic resin)
Ultem 1010-1000: trade name, SABIC Innovative Plastics Japan company makes, polyetherimide resin, 223 ℃ of fusing points
(resin combination 2; Thermoplastic resin mixes with thermoplastic elastomer (TPE))
XAREC C102: trade name, Idemitsu Kosen Co., Ltd. makes, syndiotactic polytyrene resin, 270 ℃ of fusing points
KRATON G-1657: trade name, Kraton Polymers company makes, the hydrogenated derivatives of s-B-S triblock copolymer, styrene amount 13 quality %
XAREC C102:KRATON G-1657=90 quality %:10 quality %
(fluorosilicone compound)
Preparation also uses the middle A of above-mentioned chemical formula (4) to be-(CH 2) 3OCH 2CF 2CF 3, B is-(CH 2) 3Si (OCH 3) 3, x is 21, y be 5 and z be 38 fluorosilicone compound.
(organic titanic compound)
Orgatics TC-750: trade name, Matsumoto Fine Chemical Co.Ltd. makes, two (ethyl acetoacetate) metatitanic acid diisopropyl ester
(organic zirconate)
Orgatics ZC-580: trade name, Matsumoto Fine Chemical Co.Ltd. makes, two (ethyl acetoacetate) zirconic acid dibutyl ester
(organo-silicon compound)
KBM-903: trade name, Shin-Etsu Chemial Co., Ltd makes, the 3-TSL 8330
Below, based on table 1 and table 2, the making of matrix membrane, the preparation of mold release compositions, coating and drying, fissility, the high-temperature capability of mold release compositions are described in detail.Need to prove that table 3 and table 4 are the tables that the comparative example corresponding with embodiments of the invention (comparative example 1～comparative example 7) are shown simultaneously and estimate.Therefore, the content that in the situation of comparative example, illustrates below the application similarly.
(making of matrix membrane)
Resin combination is supplied in
Figure BDA0000046567180000161
The single screw extrusion machine of L/D=25 (IKG Co., Ltd. (ア イ ケ one ジ one Co., Ltd.) manufacturing), use the full thread extrusion screw rod of compression ratio 2.5, carry out melting mixing in following barrel temperature, extrude continuously in following mold temperature by the T-die head of wide 400mm.This matrix membrane of extruding is clipped between crimping roller in the hauling machine and the chill roll cools off, in coiling machine, use the slit cutter with the both ends severing, matrix membrane is batched in batching pipe, make the matrix membrane of width 250mm, length 50m with the thickness of table 1～table 4 record thus.Herein, for resin combination 1, barrel temperature is made as 320 ℃～350 ℃, mold temperature and is made as 350 ℃～360 ℃.For resin combination 2, barrel zone temperature is made as 280 ℃～300 ℃, mold temperature and is made as 300 ℃～320 ℃.
(preparation of mold release compositions)
With the above-mentioned fluorosilicone compound of isopropanol, the preparation solid component concentration is the solution of 10 quality %.Next, with respect to the solid constituent of this solution,, prepare mold release compositions respectively with composition interpolation organic titanic compound, organic zirconate, the organo-silicon compound of table 1～table 4 record.
(coating of mold release compositions and drying)
Using scraping strip coating machine, is the wet coating thickness of table 1～table 4 record at single face coating mold release compositions to the thickness of the matrix membrane of producing.Select scraping strip coating machine in the mode that can obtain desired wet coating thickness.Next, in being adjusted to 150 ℃ the hot-air oven of band exhaust outlet, carry out drying.Be 2 minutes, 5 minutes, 10 minutes and 15 minutes drying time, produces demoulding film respectively.Herein, the calculated value that thickness calculates for the solid component concentration by wet coating thickness and mold release compositions after the drying of table 1 record.
(fissility)
For fissility, the demoulding is estimated with film and as the fissility between the epoxy resin of moulding resin.Place epoxy sealing material KMC-284 (Shin-Etsu Chemial Co., Ltd's manufacturing) in the demoulding on the face that is coated with mold release compositions of film, hold them in inner face through between 2 flat metal moulds of hard plating, carry out the hot pressing moulding, to the lamination product that mold, the demoulding estimates with the fissility between film and the epoxy resin.
Hot pressing is molded over 200 ℃ of temperature, pressure 50kg/cm 2, implement under 3 minutes the condition.And about the evaluation of fissility, the epoxy resin after the curing does not residue on the film and strippable information slip is shown " zero ", and the epoxy resin after the curing residues in the demoulding and is shown " * " with the information slip on the film.
(high-temperature capability)
For high-temperature capability, by in the Measurement of Dynamic Viscoelasticity of matrix membrane in the film of 200 ℃ of temperature in length and breadth the storage modulus E ' of two directions estimate high-temperature capability.Its reason is, the demoulding that is installed in the moulding-forming equipment enters in the molding die with film, through vacuum draw, with the molding die driving fit, so is suitable as the index of 200 ℃ high-temperature capability in the Measurement of Dynamic Viscoelasticity in 200 ℃ storage modulus E '.
Specifically, the SOLIDS ANALYZER RSAII (trade name) that uses Rheometrics company to make, the film that determines 200 ℃ of temperature under the condition of frequency 1Hz, 5 ℃/minute of programming rates, strain 0.1% is the storage modulus E ' of two directions in length and breadth.Storage modulus E ' is preferably 5.0 * 10 7Pa～3.0 * 10 9Pa, more preferably 5.0 * 10 7Pa～2.0 * 10 9The scope of Pa.When storage modulus E ' less than 5.0 * 10 7During Pa, a little less than the strain, the pressure of moulding resin causes the film breakage during use, the high-temperature capability deficiency.On the contrary, when storage modulus E ' greater than 3.0 * 10 9During Pa, though high-temperature capability fully obtains, strain is strong excessively, and following of molding die become insufficient.
By such result as can be known, like that, the sample of uncoated mold release compositions can't obtain fissility shown in comparative example 1.Like that, the sample that is coated with the less mold release compositions of the content of organic titanic compound and organic zirconate can't obtain fissility shown in comparative example 2, comparative example 3 and comparative example 4.Like that, in the time of dry 15 minutes, the thicker sample of dry back thickness can't obtain fissility in the coating back shown in comparative example 5.In the comparative example 6, the sample of the ETFE film made from Asahi Glass Co., Ltd, the thickness 50 μ m of Aflex (trade name) is a comparison other, but during the fissility under 200 ℃ of conditions estimates, film fusing.And, compare with embodiment obviously not in suitable scope as the storage modulus E ' of high-temperature capability index.In the comparative example 7, with releasing agent, the DAIFREE of Daikin Industries manufacturing TMGF-6332 (trade name, solid component concentration 3 quality %) is the comparison other of mold release compositions, but can't obtain fissility.
With respect to this, the demoulding of various embodiments of the present invention has not only obtained fissility with film, and has high-temperature capability.Thus, according to the present invention, can obtain with the fissility excellence of the resulting moulding product of moulding resin processing and forming and demoulding film with 200 ℃ of high-temperature capabilitys under the condition.
More than, use embodiment that the present invention has been described, be self-evident but technical scope of the present invention is not limited to the scope this point that above-mentioned embodiment puts down in writing.It will be apparent to one skilled in the art that and to apply various distortion or improvement to above-mentioned embodiment.And according to the record of claims, the form that has obviously applied such distortion or improvement is also contained in the technical scope of the present invention.
[table 1]
Figure BDA0000046567180000181
[table 2]
Figure BDA0000046567180000182
Figure BDA0000046567180000191
[table 3]
Figure BDA0000046567180000192
[table 4]
Figure BDA0000046567180000193

Claims (9)

1. demoulding film, it is characterized in that, to comprise the resin combination moulding of thermoplastic resin or will be that principal component and the resin combination moulding that is mixed with thermoplastic elastomer (TPE) obtain film with the thermoplastic resin, one side at least at resulting film is formed with by being coated with mold release compositions and carrying out the fluorosilicone compound layer that drying obtains, and this mold release compositions contains the fluorosilicone compound that has the silicyl that contains water-disintegrable position in molecule.
2. demoulding film as claimed in claim 1 is characterized in that, described film is made of monofilm or two-layer above multilayer film.
3. demoulding film as claimed in claim 1 or 2, it is characterized in that described thermoplastic resin is a polyphenylene sulfide, polysulfone resin, polyethersulfone resin, polyether-ether-ketone resin, polyimide resin, polyamide-imide resin, polyetherimide resin, the PEN resin, polyamide, polyacetal resin, polycarbonate resin, polyphenylene oxide resin, the polybutylene terephthalate (PBT) resin, pet resin, cyclic polyolefin resin, the syndiotactic polytyrene resin, the polymethylpentene resin, plexiglass, polyvinyl resin, acrylic resin, polystyrene resin, vinylite, at least a resin among acrylonitrile butadiene styrene resin and the AS resin acrylonitrile styrene resin; Described thermoplastic elastomer (TPE) is at least a elastomer among polyester based elastomers, polyamide-based elastomer, polyurethane series elastomer, styrene series elastomer and the olefin-based elastomer.
4. demoulding film as claimed in claim 1, it is characterized in that, described mold release compositions has the fluorosilicone compound of the silicyl that contains water-disintegrable position with respect to 100 mass parts in molecule, contain a kind of compound or the two or more compound that is selected from the group of being made up of organic titanic compound, organic zirconate and organo-silicon compound with the scope of 0.05 mass parts～20 mass parts.
5. demoulding film as claimed in claim 1, it is characterized in that, described mold release compositions has the fluorosilicone compound of the silicyl that contains water-disintegrable position with respect to 100 mass parts in molecule, contain a kind of compound or the two or more compound that is selected from the group of being made up of organic titanic compound and organic zirconate with the scope of 0.05 mass parts～20 mass parts.
6. demoulding film as claimed in claim 1, it is characterized in that, described mold release compositions has the fluorosilicone compound of the silicyl that contains water-disintegrable position in molecule with respect to 100 mass parts, scope with 0.05 mass parts～20 mass parts contains a kind of compound or the two or more compound that is selected from the group of being made up of organic titanic compound and organic zirconate, and contains organo-silicon compound with the scope of 0.05 mass parts～20 mass parts.
7. demoulding film as claimed in claim 1 is characterized in that,
Describedly will comprise the resin combination moulding of thermoplastic resin or will be that the thickness of the monofilm that obtains of principal component and the resin combination moulding that is mixed with thermoplastic elastomer (TPE) or two-layer above multilayer film is the scope of 5 μ m～500 μ m with the thermoplastic resin;
Described is the scope of 0.05 μ m～10 μ m by coating mold release compositions and the thickness that carries out the fluorosilicone compound layer that drying obtains, and this mold release compositions contains the fluorosilicone compound that has the silicyl that contains water-disintegrable position in molecule.
8. the demoulding is characterized in that comprising following operation with the manufacture method of film:
Prepare film, this film is to comprise the resin combination moulding of thermoplastic resin or will be the film that principal component and the resin combination moulding that is mixed with thermoplastic elastomer (TPE) obtain with the thermoplastic resin;
One side at least at this film is coated with mold release compositions and carries out drying, forms the fluorosilicone compound layer, and described mold release compositions contains the fluorosilicone compound that has the silicyl that contains water-disintegrable position in molecule.
9. the demoulding as claimed in claim 8 is characterized in that with the manufacture method of film described film comprises monofilm or two-layer above multilayer film.
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CN104768760A (en) * 2013-01-11 2015-07-08 尤尼吉可株式会社 Releasing film and method producing the same
CN105619666A (en) * 2016-03-18 2016-06-01 常州大学 Preparation method for reusable water-based release agent having rheological property
CN106132657A (en) * 2013-12-24 2016-11-16 全耐塑料公司 The plastic semi-finished product preforming of film auxiliary
CN109312087A (en) * 2016-07-04 2019-02-05 Ａｇｃ株式会社 Ethylene-tetrafluoroethylene copolymer film and its manufacturing method
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CN103254612A (en) * 2012-02-20 2013-08-21 信越聚合物株式会社 Mold release film
CN103254612B (en) * 2012-02-20 2015-05-27 信越聚合物株式会社 Mold release film
CN104768760A (en) * 2013-01-11 2015-07-08 尤尼吉可株式会社 Releasing film and method producing the same
CN104768760B (en) * 2013-01-11 2017-06-09 尤尼吉可株式会社 Mold release film and its manufacture method
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CN104425290A (en) * 2013-08-27 2015-03-18 硕正科技股份有限公司 Debonding component applied to wafer packaging
CN106132657A (en) * 2013-12-24 2016-11-16 全耐塑料公司 The plastic semi-finished product preforming of film auxiliary
CN105619666A (en) * 2016-03-18 2016-06-01 常州大学 Preparation method for reusable water-based release agent having rheological property
CN105619666B (en) * 2016-03-18 2017-12-01 常州大学 A kind of preparation of the reusable aqueous release agent with rheological characteristic
CN109312087A (en) * 2016-07-04 2019-02-05 Ａｇｃ株式会社 Ethylene-tetrafluoroethylene copolymer film and its manufacturing method
CN109312087B (en) * 2016-07-04 2022-04-05 Ａｇｃ株式会社 Ethylene-tetrafluoroethylene copolymer film and method for producing same
CN113423563A (en) * 2018-12-19 2021-09-21 科思创知识产权两合公司 Method for preparing polyurethane composite material by vacuum infusion process

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JP5165715B2 (en) 2013-03-21
CN102198714B (en) 2014-04-30

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