TW202330223A - Mold release film for molding of resin sheet - Google Patents
Mold release film for molding of resin sheet Download PDFInfo
- Publication number
- TW202330223A TW202330223A TW112110578A TW112110578A TW202330223A TW 202330223 A TW202330223 A TW 202330223A TW 112110578 A TW112110578 A TW 112110578A TW 112110578 A TW112110578 A TW 112110578A TW 202330223 A TW202330223 A TW 202330223A
- Authority
- TW
- Taiwan
- Prior art keywords
- release layer
- release
- film
- cation
- mass
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 115
- 239000011347 resin Substances 0.000 title claims abstract description 115
- 238000000465 moulding Methods 0.000 title abstract description 36
- 239000010410 layer Substances 0.000 claims abstract description 333
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 176
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 98
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 98
- 239000000919 ceramic Substances 0.000 claims abstract description 86
- 239000002344 surface layer Substances 0.000 claims abstract description 69
- 229920006267 polyester film Polymers 0.000 claims abstract description 35
- 239000010954 inorganic particle Substances 0.000 claims abstract description 19
- 230000003746 surface roughness Effects 0.000 claims abstract description 18
- 239000011254 layer-forming composition Substances 0.000 claims description 88
- 150000001875 compounds Chemical class 0.000 claims description 48
- 238000004519 manufacturing process Methods 0.000 claims description 38
- 125000003700 epoxy group Chemical group 0.000 claims description 30
- 125000002723 alicyclic group Chemical group 0.000 claims description 27
- 125000002091 cationic group Chemical group 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 24
- 150000002484 inorganic compounds Chemical class 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 13
- 229910010272 inorganic material Inorganic materials 0.000 claims description 12
- 125000003566 oxetanyl group Chemical group 0.000 claims description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 35
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- 238000000034 method Methods 0.000 description 29
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
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- 238000001723 curing Methods 0.000 description 23
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- 239000002904 solvent Substances 0.000 description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 22
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- 238000012545 processing Methods 0.000 description 21
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- 239000002253 acid Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
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- 230000002776 aggregation Effects 0.000 description 13
- 239000002002 slurry Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 description 11
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- 238000004220 aggregation Methods 0.000 description 10
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- 238000004132 cross linking Methods 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 4
- 229910002113 barium titanate Inorganic materials 0.000 description 4
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- 239000012634 fragment Substances 0.000 description 4
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 150000004010 onium ions Chemical class 0.000 description 4
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
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- 239000000314 lubricant Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004421 molding of ceramic Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- VRFOKYHDLYBVAL-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CCN1C=C[N+](C)=C1 VRFOKYHDLYBVAL-UHFFFAOYSA-M 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
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- 241000234282 Allium Species 0.000 description 1
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- 208000032544 Cicatrix Diseases 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
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Abstract
Description
本發明係關於一種樹脂片成型用離型膜,更詳而言之係關於一種於成型出超薄層之樹脂片時所使用之離型膜。The present invention relates to a release film for forming a resin sheet, and more specifically relates to a release film used when forming an ultra-thin layer of resin sheet.
以往,以聚酯膜作為基材並於該基材上積層有離型層之離型膜係當作黏著片係當作用以成型出覆膜、高分子膜、光學透鏡等樹脂片的步驟膜來使用。In the past, a polyester film was used as a base material and a release film layered on the base material was used as an adhesive sheet system as a step film for molding resin sheets such as coatings, polymer films, and optical lenses. to use.
前述離型膜也當作積層陶瓷電容器、陶瓷基板等要求高平滑性之陶瓷生坯成型用步驟膜來使用。近年,伴隨積層陶瓷電容器之小型化/高容量化,陶瓷生坯之厚度也有薄膜化的傾向。陶瓷生坯係將含有鈦酸鋇等陶瓷成分與黏結劑樹脂的漿料塗敷於離型膜上並乾燥來被成型。對於成型後的陶瓷生坯印刷電極並自離型膜剝離所得之陶瓷生坯係經過積層、加壓、燒成、外部電極塗布來製造出積層陶瓷電容器。The aforementioned release film is also used as a step film for ceramic green molding that requires high smoothness, such as multilayer ceramic capacitors and ceramic substrates. In recent years, along with miniaturization and higher capacity of multilayer ceramic capacitors, the thickness of ceramic green sheets tends to be thinner. The ceramic green body is molded by coating a slurry containing ceramic components such as barium titanate and a binder resin on a release film and drying it. The formed ceramic green body is printed with electrodes and peeled off from the release film. The resulting ceramic green body is laminated, pressed, fired, and coated with external electrodes to manufacture a multilayer ceramic capacitor.
於聚酯膜基材之離型層表面成型出陶瓷生之情況,離型層表面之微小突起會對於所成型之陶瓷生坯造成影響,而容易產生縮孔(cissing)或針孔等缺點,此為問題所在。近年來,邁向進一步的陶瓷生坯薄膜化,而逐漸要求1.0μm以下、更詳而言之為0.2μm至1.0μm之厚度的陶瓷生坯。為此,關於離型層表面之平滑性的要求更為提高。此外,離型層上的極微小突起、異物涉及到所成型之陶瓷生坯之變形,而存在有變得容易產生針孔、剝離時之破片等之課題。In the case of forming a ceramic green body on the surface of the release layer of the polyester film substrate, the tiny protrusions on the surface of the release layer will affect the formed ceramic green body, and easily produce defects such as shrinkage cavities (cissing) or pinholes. This is the problem. In recent years, further thinning of the ceramic green body is being pursued, and a ceramic green body having a thickness of 1.0 μm or less, more specifically, 0.2 μm to 1.0 μm, is increasingly required. For this reason, the requirements for the smoothness of the surface of the release layer are even higher. In addition, microscopic protrusions and foreign matter on the release layer are involved in deformation of the molded ceramic green body, and there are problems that pinholes and fragments during peeling are likely to occur.
此外,一旦邁向陶瓷生坯薄膜化,從離型膜剝離陶瓷生坯時的剝離性變得更為重要。若剝離力大、不均勻則於剝離步驟中會對陶瓷生坯造成損傷,而發生片缺陷、厚度不均等,產生針孔、產生破片等不佳情形,此為問題所在。因此,要求能以更低而均勻的力來剝離陶瓷生坯。亦即,為了無缺陷地製造超薄層之樹脂片、尤其是無缺陷地製造陶瓷生坯,具有極高平滑性以及優異剝離性之離型膜成為必要。In addition, as the ceramic green body becomes thinner, the peelability at the time of peeling the ceramic green body from the release film becomes more important. If the peeling force is large and uneven, the ceramic green body will be damaged during the peeling step, and sheet defects, uneven thickness, etc., pinholes, and fragments will occur. This is the problem. Therefore, it is required to be able to peel off the ceramic green body with a lower and uniform force. That is, in order to produce an ultra-thin resin sheet without defects, especially a ceramic green body without defects, a release film having extremely high smoothness and excellent peelability is required.
作為平滑性與剝離性優異之離型膜,可舉出以下所記載之專利文獻者。例如專利文獻1中提議了一種具有使用自由基硬化型樹脂作為主成分之離型層的離型膜。專利文獻2中提議了一種有平滑化層與離型層所積層而構成之離型膜。專利文獻3中提議了一種具有使用陽離子硬化型環氧樹脂作為主成分之離型層的離型膜。專利文獻4中提議了一種具有使用陽離子硬化型聚二甲基矽氧烷作為主成分之離型層的離型膜。 [先前技術文獻] [專利文獻] As a release film excellent in smoothness and peelability, what is described in the following patent documents is mentioned. For example, Patent Document 1 proposes a release film having a release layer mainly composed of a radical-curable resin. Patent Document 2 proposes a release film formed by laminating a smoothing layer and a release layer. Patent Document 3 proposes a release film having a release layer using a cation-curing epoxy resin as a main component. Patent Document 4 proposes a release film having a release layer using cation-curable polydimethylsiloxane as a main component. [Prior Art Literature] [Patent Document]
[專利文獻1]日本專利第5492352號。 [專利文獻2]日本特開2015-164762號公報。 [專利文獻3]國際公開第2018/079337。 [專利文獻4]日本特開2016-079349號公報。 [Patent Document 1] Japanese Patent No. 5492352. [Patent Document 2] Japanese Patent Laid-Open No. 2015-164762. [Patent Document 3] International Publication No. 2018/079337. [Patent Document 4] Japanese Patent Laid-Open No. 2016-079349.
[發明所欲解決之課題][Problem to be Solved by the Invention]
但是,專利文獻1之離型膜由於對於平滑性不充分的基材膜設置離型層,而有離型層之平滑性不充分之課題。再者,本發明人等經過努力研究的結果,發現自由基硬化型之樹脂由於氧阻礙而發生硬化不良,故離型層表面之耐溶劑性差,離型層會因為陶瓷生坯之成型時或內部電極印刷時所使用之有機溶媒而被侵蝕,而有剝離性變差的問題。 專利文獻2之發明在平滑化塗布層與離型塗布層使用了熱硬化性三聚氰胺樹脂,為了促進硬化反應需要高熱量。因此,有離型膜之平面性因加工時之熱而受損之虞。此外,由於需要平滑化塗布層與離型塗布層之複數加工,故不僅有異物混入離型膜之虞,尚有離型層出現傷痕之虞,擔心成型在離型層上的陶瓷生坯會被轉印異物或傷痕而發生不佳情況。 However, the release film of Patent Document 1 has a problem that the smoothness of the release layer is insufficient because the release layer is provided on the base film having insufficient smoothness. Furthermore, the present inventors have worked hard to find that free radical hardening resins are poorly cured due to oxygen hindrance, so the solvent resistance on the surface of the release layer is poor, and the release layer will be damaged due to the molding of the ceramic green body or The organic solvent used for internal electrode printing is corroded, resulting in poor peelability. The invention of Patent Document 2 uses a thermosetting melamine resin for the smoothing coating layer and the release coating layer, and high heat is required to accelerate the curing reaction. For this reason, the planarity of a release film may be impaired by the heat at the time of processing. In addition, due to the need for multiple processing of the smoothing coating layer and the release coating layer, not only the foreign matter may be mixed into the release film, but also the release layer may be scratched, and the ceramic green body molded on the release layer may be damaged. Defects occur due to transfer of foreign matter or scratches.
專利文獻3、專利文獻4為了改善源自氧阻礙之硬化不良、加工熱所致平面不良,分別提議了使用陽離子硬化型樹脂的離型層。但是,專利文獻3之離型膜由於欠缺基材膜之平滑性,而有離型層表面之平滑性差的問題。此外,專利文獻3中所揭示之離型劑成分缺乏反應性,耐溶劑性差且剝離性也有問題。 專利文獻4之離型膜由於具有使用液狀陽離子硬化型聚二甲基矽氧烷樹脂作為主成分之離型層,樹脂會凝聚於基材膜之凹凸、基材膜表面所存在之寡聚物等突起處,恐發生平面性的問題。此外,離型層之交聯密度低,在剝離性方面也有問題。 Patent Document 3 and Patent Document 4 respectively propose release layers using cation-curable resins in order to improve hardening defects due to oxygen barriers and planar defects caused by processing heat. However, the release film of Patent Document 3 lacks the smoothness of the base film and has a problem of poor smoothness on the surface of the release layer. In addition, the release agent component disclosed in Patent Document 3 lacks reactivity, has poor solvent resistance, and has problems with peelability. Since the release film of Patent Document 4 has a release layer using a liquid cationic hardening type polydimethylsiloxane resin as the main component, the resin will condense on the unevenness of the base film and the oligomers present on the surface of the base film. Objects and other protrusions may cause flatness problems. In addition, the crosslink density of the release layer is low, and there is also a problem in peelability.
本發明係以相關習知技術之課題為背景而得。亦即,目的在於可提供一種具有特別在平滑性與剝離性優異之離型層的離型膜,再者,可提供一種可無缺陷地成型出超薄層之樹脂片、特別是超薄層之陶瓷生坯的離型膜。 [用以解決課題之手段] The present invention is made on the basis of the subject of related prior art. That is, the purpose is to provide a release film with a release layer that is particularly excellent in smoothness and peelability, and to provide a resin sheet that can form an ultra-thin layer without defects, especially an ultra-thin layer. The release film of the ceramic green body. [Means to solve the problem]
本發明人等為了解決上述課題經過努力研究的結果,發現依據具有下述構成之離型膜可達成前述目的,從而完成了本發明。As a result of diligent research by the present inventors to solve the above-mentioned problems, they found that the above-mentioned object can be achieved by a release film having the following constitution, and completed the present invention.
亦即,本發明具有以下構成。 [1]一種樹脂片成型用離型膜,具有作為基材之聚酯膜以及離型層;前述聚酯膜具有實質上不含無機粒子之表面層A;於前述表面層A上具有前述離型層;前述離型層係離型層形成組成物經硬化之層;前述離型層形成組成物含有陽離子硬化型聚二甲基矽氧烷(a);前述離型層之區域表面粗度(Sa)為2nm以下;存在於前述離型層表面之高度10nm以上之突起數為200個/mm 2以下。 [2]於一實施態樣中,前述離型層之最大突起高度(Sp)為20nm以下,存在於離型層表面之高度5nm以上至未達10nm之突起數與前述10nm以上之突起數之合計為1500個/mm 2以下。 [3]於一實施態樣中,陽離子硬化型聚二甲基矽氧烷(a)至少具有一個選自乙烯醚基、氧雜環丁基、環氧基、脂環式環氧基之官能基。 [4]於一實施態樣中,離型層所含陽離子硬化型聚二甲基矽氧烷(a)之含量為90mg/m 2以下。 [5]於一實施態樣中,離型層形成組成物進而含有不具聚矽氧骨架之陽離子硬化型化合物(b-1);陽離子硬化型化合物(b-1)於分子內具有2個以上之脂環式環氧基,相對於陽離子硬化型聚二甲基矽氧烷(a)與陽離子硬化型化合物(b-1)之合計100質量份,陽離子硬化型化合物(b-1)之含量為80質量%以上。 [6]於一實施態樣中,離型層形成組成物進而含有具脂環式環氧基之環狀矽氧烷化合物(b-2);環狀矽氧烷化合物(b-2)於分子內具有2個以上之脂環式環氧基,相對於陽離子硬化型聚二甲基矽氧烷(a)與環狀矽氧烷化合物(b-2)之合計100質量份,環狀矽氧烷化合物(b-2)之含量為80質量%以上。 [7]於一實施態樣中,離型層形成組成物含有SP值(δ)為14以上至17以下之有機溶媒,離型層形成組成物中,相對於離型層形成組成物之總重量100質量份以10質量%以上之量含有SP值(δ)為14以上至17以下之前述有機溶媒。 [8]於一實施態樣中,提供一種離型膜,係用以製造含無機化合物之樹脂片。 [9]於一實施態樣中,含無機化合物之樹脂片為陶瓷生坯。 [10]於一實施態樣中,提供一種離型膜,係用以成型出厚度為0.2μm以上至1.0μm以下之樹脂片。 [發明功效] That is, the present invention has the following constitutions. [1] A release film for forming a resin sheet, comprising a polyester film as a base material and a release layer; the polyester film has a surface layer A substantially free of inorganic particles; Type layer; the aforementioned release layer is a hardened layer of the release layer forming composition; the aforementioned release layer forming composition contains cationic hardening polydimethylsiloxane (a); the surface roughness of the aforementioned release layer (Sa) is 2 nm or less; the number of protrusions with a height of 10 nm or more existing on the surface of the release layer is 200/mm 2 or less. [2] In one embodiment, the maximum protrusion height (Sp) of the release layer is 20 nm or less, and the ratio of the number of protrusions with a height of 5 nm or more to less than 10 nm existing on the surface of the release layer to the number of protrusions of 10 nm or more The total is 1500 pieces/mm 2 or less. [3] In one embodiment, the cationic hardening polydimethylsiloxane (a) has at least one functional group selected from vinyl ether group, oxetanyl group, epoxy group, and alicyclic epoxy group. base. [4] In one embodiment, the content of the cation-curable polydimethylsiloxane (a) contained in the release layer is 90 mg/m 2 or less. [5] In one embodiment, the release layer forming composition further contains a cation-curable compound (b-1) that does not have a polysiloxane skeleton; the cation-curable compound (b-1) has two or more The alicyclic epoxy group, the content of the cation-curable compound (b-1) relative to the total of 100 parts by mass of the cation-curable polydimethylsiloxane (a) and the cation-curable compound (b-1) It is more than 80% by mass. [6] In one embodiment, the release layer forming composition further contains a cyclic siloxane compound (b-2) having an alicyclic epoxy group; the cyclic siloxane compound (b-2) is Having two or more alicyclic epoxy groups in the molecule, cyclic silicon is The content of the oxane compound (b-2) is 80% by mass or more. [7] In one embodiment, the release layer-forming composition contains an organic solvent with an SP value (δ) of 14 to 17. In the release layer-forming composition, relative to the total amount of the release layer-forming composition 100 parts by mass by weight contain the aforementioned organic solvent having an SP value (δ) of 14 or more and 17 or less in an amount of 10 mass % or more. [8] In one embodiment, a release film is provided, which is used to manufacture a resin sheet containing an inorganic compound. [9] In one embodiment, the resin sheet containing the inorganic compound is a ceramic green body. [10] In one embodiment, a release film is provided, which is used to form a resin sheet with a thickness of not less than 0.2 μm and not more than 1.0 μm. [Efficacy of the invention]
本發明之樹脂片成型用離型膜可提高離型層之平滑性與剝離性,進而可抑制超薄層樹脂片、尤其是陶瓷生坯之缺陷的發生。The release film for resin sheet molding of the present invention can improve the smoothness and peelability of the release layer, and further suppress the occurrence of defects in ultra-thin layer resin sheets, especially ceramic green bodies.
以下,針對本發明詳細說明。 本發明為一種樹脂片成型用離型膜,具有作為基材之聚酯膜以及離型層;聚酯膜具有實質上不含無機粒子之表面層A;於表面層A上具有離型層;離型層為離型層形成組成物經硬化之層;離型層形成組成物含有陽離子硬化型聚二甲基矽氧烷(a);離型層之區域表面粗度(Sa)為2nm以下;存在於離型層表面之高度10nm以上之突起數為200個/mm 2以下。 Hereinafter, the present invention will be described in detail. The present invention is a release film for forming a resin sheet, which has a polyester film as a base material and a release layer; the polyester film has a surface layer A substantially free of inorganic particles; the surface layer A has a release layer; The release layer is a hardened layer of the release layer forming composition; the release layer forming composition contains cationic hardening polydimethylsiloxane (a); the surface roughness (Sa) of the release layer is less than 2nm ; The number of protrusions with a height of 10 nm or more existing on the surface of the release layer is 200/mm 2 or less.
具有此種構成之本案發明由於離型層之平滑性與剝離性優異,故對於例如厚度為0.2μm至1.0μm以下之樹脂片,可無缺陷地提供均勻厚度,可抑制針孔等缺點。 此外,本案發明可發揮以下效果。本發明由於對於平滑性充分的基材膜設置離型層,故亦可確保離型層之平滑性。進而本發明於離型層可抑制氧阻礙所致硬化不良,可發揮離型層之高交聯。可發揮此種效果之本發明例如可提高離型層表面之耐溶劑性。藉由提高離型層表面之耐溶劑性,可抑制於陶瓷生坯成型時、內部電極之印刷時所使用之有機溶媒造成離型層受到侵蝕,具有高剝離性。 此外,若為本發明,相較於例如具有熱硬化性三聚氰胺樹脂之離型層,為了促進硬化反應無須高熱。因此,可抑制加工時之熱而損及離型膜之平面性。此外,若為本發明之製造方法,藉由經過本發明之塗布步驟、乾燥步驟,可抑制離型層形成組成物凝聚,可獲得具備具極高平滑性之離型層的離型膜。 The present invention having such a structure can provide a uniform thickness without defects for a resin sheet with a thickness of 0.2 μm to less than 1.0 μm, and can suppress defects such as pinholes, because the release layer has excellent smoothness and peelability. In addition, the present invention can exhibit the following effects. In the present invention, since a release layer is provided on a base film having sufficient smoothness, the smoothness of the release layer can also be ensured. Furthermore, the present invention can suppress poor hardening caused by oxygen hindrance in the release layer, and can exert high cross-linking of the release layer. This invention which can exhibit such an effect can improve the solvent resistance of the release layer surface, for example. By improving the solvent resistance of the surface of the release layer, it is possible to prevent the release layer from being corroded by the organic solvent used in the molding of the ceramic green body and the printing of the internal electrodes, and has high peelability. Moreover, according to this invention, compared with the release layer which has a thermosetting melamine resin, for example, high heat is not needed in order to accelerate hardening reaction. Therefore, the heat during processing can be suppressed from impairing the planarity of the release film. In addition, according to the production method of the present invention, by passing through the coating step and the drying step of the present invention, aggregation of the composition for forming the release layer can be suppressed, and a release film having a release layer with extremely high smoothness can be obtained.
更詳細來說,藉由對於基材膜的實質上不含無機粒子之表面層A塗布含有預定量之陽離子硬化型聚二甲基矽氧烷(a)的離型層形成用組成物並使之硬化,可獲得具有極高平滑性之離型層。 進而,藉由將離型層中之陽離子硬化型聚二甲基矽氧烷(a)之含量控制在預定量以下,於離型層之加工時,可抑制陽離子硬化型聚二甲基矽氧烷(a)對存在於基材膜之極微小異物、源自寡聚物之微小突起產生凝聚。雖不應限定於特定的理論來解釋,藉由提高第1乾燥溫度(加強乾燥)可防止成分(a)對於起因於原輥體的微細突起產生凝聚。 此外,藉由抑制氧阻礙所致硬化不良、提高離型層表面之耐溶劑性、抑制異物混入離型層、以及抑制離型層之傷痕,可防止對於陶瓷生坯等之被離型體造成剝離時之損傷、傷痕、異物等因轉印所致片變形。其結果,可獲得平滑性與硬度、剝離性、對被離型層之污染防止性優異之離型層。 此外,於離型層形成組成物中所含有機溶媒之乾燥中,陽離子硬化型聚二甲基矽氧烷(a)變得不易凝聚,可做成平滑性優異之離型層。詳細如後述。 More specifically, by applying a composition for forming a release layer containing a predetermined amount of cation-curable polydimethylsiloxane (a) to the surface layer A of the base film that does not substantially contain inorganic particles, and using Hardening can obtain a release layer with extremely high smoothness. Furthermore, by controlling the content of the cation-curable polydimethylsiloxane (a) in the release layer to be below a predetermined amount, the cation-curable polydimethylsiloxane can be suppressed during the processing of the release layer. The alkane (a) aggregates microscopic foreign matter present in the substrate film and microscopic protrusions derived from oligomers. Although the explanation should not be limited to a specific theory, by raising the first drying temperature (enhanced drying), it is possible to prevent component (a) from coagulating on the fine protrusions caused by the original roll body. In addition, by suppressing poor hardening caused by oxygen inhibition, improving the solvent resistance of the surface of the release layer, suppressing the incorporation of foreign matter into the release layer, and suppressing the scratches of the release layer, it is possible to prevent damage to the release material such as ceramic green bodies. Deformation of the sheet due to transfer printing, such as damage, scars, and foreign matter during peeling. As a result, a release layer excellent in smoothness, hardness, releasability, and contamination prevention of the release layer can be obtained. In addition, during drying of the organic solvent contained in the release layer forming composition, the cation-curable polydimethylsiloxane (a) becomes less likely to aggregate, and a release layer excellent in smoothness can be formed. Details will be described later.
此外,本發明於其他態樣中係提供一種具有以下步驟之樹脂片成型用離型膜之製造方法。 塗布步驟,係於具有表面層A之聚酯膜之前述表面層A上塗布離型層形成組成物,表面層A為實質上不含無機粒子之層,離型層形成組成物含有陽離子硬化型聚二甲基矽氧烷(a);乾燥步驟,將塗布有離型層形成組成物之聚酯膜加以加熱乾燥,前述加熱乾燥具有第1乾燥步驟以及接續之第2乾燥步驟,前述第1乾燥步驟中之乾燥溫度T1高於前述第2乾燥步驟中之乾燥溫度T2;以及,光硬化步驟,係於前述乾燥步驟後照射活性能量線,使得離型層形成組成物硬化。 Moreover, this invention provides the manufacturing method of the release film for resin sheet molding which has the following steps in another aspect. The coating step is to apply a release layer forming composition on the aforementioned surface layer A of the polyester film having a surface layer A. The surface layer A is a layer substantially free of inorganic particles, and the release layer forming composition contains a cationic hardening type Polydimethylsiloxane (a); drying step, heating and drying the polyester film coated with the release layer forming composition, the aforementioned heating drying has a first drying step and a subsequent second drying step, the aforementioned first The drying temperature T1 in the drying step is higher than the drying temperature T2 in the second drying step; and, the photocuring step is to irradiate active energy rays after the drying step to harden the release layer forming composition.
本發明相關之製造方法中,特別藉由將加工離型層時之製造條件設定為預定方法,可形成具有高平滑之離型層。例如可舉出控制離型層形成用組成物之塗布量、有機溶媒組成、乾燥時間、乾燥溫度等。藉由以本案發明之條件來製造離型膜,可抑制離型層形成用組成物中所含陽離子硬化型聚二甲基矽氧烷(a)之凝聚,可得到平滑性優異之離型層。詳細如後述。In the manufacturing method related to the present invention, in particular, by setting the manufacturing conditions when processing the release layer to a predetermined method, a release layer having high smoothness can be formed. For example, control of the coating amount of the release layer forming composition, organic solvent composition, drying time, drying temperature, etc. is mentioned. By producing the release film under the conditions of the present invention, the aggregation of the cation-curable polydimethylsiloxane (a) contained in the composition for forming the release layer can be suppressed, and a release layer with excellent smoothness can be obtained . Details will be described later.
(聚酯膜) 構成本發明之基材所使用之聚酯膜的聚酯並無特別限定,可使用將作為離型膜用基材通常一般所使用的聚酯加以膜成形而得者。較佳為由芳香族二元酸成分與二醇成分所構成之結晶性線狀飽和聚酯,例如聚對苯二甲酸乙二酯、聚萘二甲酸-2,6-乙二酯、聚對苯二甲酸丁二酯、聚對苯二甲酸丙二酯或是以此等樹脂之構成成分作為主成分之共聚物為更適宜,尤其是聚對苯二甲酸乙二酯所形成之聚酯膜為特別適宜。聚對苯二甲酸乙二酯中,對苯二甲酸乙二酯之重複單元較佳為90莫耳%以上,更佳為95莫耳%以上,亦可少量共聚其他二羧酸成分、二醇成分,但以成本考量,較佳為僅由對苯二甲酸與乙二醇所製造者。此外,在不妨礙本發明之膜效果的範圍內,亦可添加公知的添加劑,例如抗氧化劑、光穩定劑、紫外線吸收劑、結晶化劑等。基於聚酯膜在兩方向之彈性模數的高低等理由,較佳為雙軸配向聚酯膜。 (polyester film) The polyester constituting the polyester film used for the base material of the present invention is not particularly limited, and a polyester generally used as a base material for a release film by film-forming can be used. It is preferably a crystalline linear saturated polyester composed of an aromatic dibasic acid component and a diol component, such as polyethylene terephthalate, polyethylene naphthalate-2,6-ethylene glycol, polyethylene terephthalate Butyl phthalate, polytrimethylene terephthalate, or copolymers with these resin components as the main component are more suitable, especially polyester films formed of polyethylene terephthalate is particularly suitable. In polyethylene terephthalate, the repeating unit of ethylene terephthalate is preferably more than 90 mole%, more preferably more than 95 mole%. A small amount of other dicarboxylic acid components and diols can also be copolymerized components, but considering the cost, it is better to manufacture only terephthalic acid and ethylene glycol. In addition, known additives such as antioxidants, photostabilizers, ultraviolet absorbers, crystallizers, and the like may be added within the range that does not hinder the film effect of the present invention. For reasons such as the elastic modulus of the polyester film in two directions, etc., a biaxially oriented polyester film is preferred.
上述聚酯膜之固有黏度以0.50 dl/g至0.70dl/g為佳,以0.52dl/g至0.62dl/g為更佳。當固有黏度為0.50dl/g以上之情況,於延伸步驟不會發生大量的斷裂故較佳。相反地,當為0.70dl/g以下之情況,裁斷成為預定製品寬度時的裁斷性良好,不會發生尺寸不良故較佳。此外,原料顆粒經充分真空乾燥為佳。 此外,本說明書中僅記載為「聚酯膜」之情況,意指具有(積層有)表面層A之聚酯膜。此外,本發明中,聚酯膜具有實質上不含無機粒子之表面層A,於表面層A上具有前述離型層。 此外,若說明書中有提及的情況,有時將進而具有(積層有)表面層B之聚酯膜簡稱為「聚酯膜」。 The intrinsic viscosity of the polyester film is preferably from 0.50 dl/g to 0.70 dl/g, more preferably from 0.52 dl/g to 0.62 dl/g. When the intrinsic viscosity is 0.50 dl/g or more, it is preferable because a large amount of fracture does not occur in the stretching step. Conversely, when it is 0.70 dl/g or less, the cutting property when cutting to a predetermined product width is good, and dimensional defects do not occur, so it is preferable. In addition, it is preferable that the raw material particles are sufficiently vacuum-dried. In addition, when only the "polyester film" is described in this specification, it means the polyester film which has (laminated) the surface layer A. Moreover, in this invention, a polyester film has the surface layer A which does not contain an inorganic particle substantially, and has the said release layer on the surface layer A. In addition, when mentioned in the specification, the polyester film which further has (laminates) the surface layer B may be abbreviated as "polyester film".
本發明中聚酯膜之製造方法並無特別限定,可使用以往一般所採用的方法。例如,將前述聚酯以擠出機進行熔融,擠出成膜狀,於旋轉冷卻轉筒進行冷卻來獲得未延伸膜,將該未延伸膜加以延伸而獲得。延伸若為雙軸延伸則在力學特性等方面來看較佳。雙軸延伸膜可藉由將縱向或是橫向之單軸延伸膜在橫向或是縱向上進行逐步雙軸延伸之方法、或是將未延伸膜在縱向與橫向進行同步雙軸延伸之方法來獲得。The method for producing the polyester film in the present invention is not particularly limited, and conventionally generally used methods can be used. For example, the aforementioned polyester is melted with an extruder, extruded into a film, cooled in a rotating cooling drum to obtain an unstretched film, and the unstretched film is stretched. When stretching is biaxial stretching, it is preferable in terms of mechanical properties and the like. A biaxially stretched film can be obtained by biaxially stretching a longitudinally or transversely uniaxially stretched film stepwise in the transverse or longitudinal direction, or by synchronously biaxially stretching an unstretched film in the longitudinal and transverse directions .
本發明中,聚酯膜延伸時之延伸溫度設為聚酯之二次轉移點(Tg)以上為佳。縱向、橫向個別方向進行以1倍至8倍、尤其是2倍至6倍之延伸為佳。In the present invention, the stretching temperature at the time of stretching the polyester film is preferably equal to or higher than the secondary transition point (Tg) of the polyester. It is better to stretch 1 to 8 times, especially 2 to 6 times in the vertical and horizontal directions.
上述聚酯膜之厚度以12μm至50μm為佳,更佳為15μm至38μm,又更佳為19μm至33μm。膜之厚度只要為12μm以上,則於膜生產時或離型層之加工步驟、陶瓷生坯等之成型時,無受熱變形之虞故較佳。另一方面,膜之厚度只要為50μm以下,則使用後廢棄之膜量不會極度變多,以減少環境負荷而言為佳。The thickness of the polyester film is preferably from 12 μm to 50 μm, more preferably from 15 μm to 38 μm, and still more preferably from 19 μm to 33 μm. As long as the thickness of the film is 12 μm or more, it is preferable because there is no risk of thermal deformation during film production, processing steps of release layer, and molding of ceramic green bodies. On the other hand, as long as the thickness of the film is 50 μm or less, the amount of film discarded after use will not increase extremely, which is preferable in terms of reducing environmental load.
上述聚酯膜可為單層,2層以上之多層亦無妨。聚酯膜具有實質上不含無機粒子之表面層A。例如,可為表面層A之單層,亦可為具有表面層A與其他層(例如後述表面層B)之多層結構。 由2層以上之多層構成所構成之積層聚酯膜之情況,於實質上不含無機粒子之表面層A之相反面以具有可含粒子等之表面層B為佳。在積層構成上,若以塗布離型層之側的層當作表面層A,將相反面之層當作表面層B,將表面層A、表面層B以外之芯層當作層C,則厚度方向之層構成可舉出離型層/A/B、或是離型層/A/C/B等之積層結構。當然層C亦可為複數之層構成。此外,表面層B亦可不含粒子。此情況下,為了在將膜捲取成輥狀時賦予滑動性,於表面層B上設置包含粒子與黏結劑之塗層為佳。 The above-mentioned polyester film may be a single layer, or a multi-layer of two or more layers may be used. The polyester film has a surface layer A substantially free of inorganic particles. For example, it may be a single layer of the surface layer A, or may be a multilayer structure having the surface layer A and other layers (for example, the surface layer B described later). In the case of a laminated polyester film composed of two or more layers, it is preferable to have a surface layer B that may contain particles on the opposite side of the surface layer A that does not substantially contain inorganic particles. In terms of laminate composition, if the layer on the side where the release layer is coated is regarded as surface layer A, the layer on the opposite side is regarded as surface layer B, and the core layer other than surface layer A and surface layer B is regarded as layer C, then The layer configuration in the thickness direction includes a laminated structure such as a release layer/A/B or a release layer/A/C/B. Of course, the layer C can also be composed of plural layers. In addition, the surface layer B may not contain particles. In this case, it is preferable to provide a coating layer containing particles and a binder on the surface layer B in order to impart slipperiness when the film is wound up into a roll.
本發明之聚酯膜,位於塗布離型層之表面處的表面層A實質上不含無機粒子。本發明中,表面層A由於實質上不含無機粒子,而可顯示出以下的區域表面平均粗度。 本發明中,表面層A之區域表面平均粗度(Sa)為配置離型層之面之中的區域表面平均粗度(Sa),配置離型層之面之中的區域表面平均粗度(Sa)為7nm以下。若Sa為7nm以下,則即使是積層於表面層A上的離型層也可展現高平滑性,在積層於離型層上之超薄層陶瓷生坯之成型時不易產生針孔等。再者,於形成離型層之際,可抑制離型層成分凝聚於表面層A上之突起,可防止離型層表面之平滑性的惡化。 In the polyester film of the present invention, the surface layer A located on the surface of the coated release layer does not substantially contain inorganic particles. In the present invention, since the surface layer A does not substantially contain inorganic particles, it can exhibit the following average surface roughness in the region. In the present invention, the area surface average roughness (Sa) of the surface layer A is the area surface average roughness (Sa) in the face where the release layer is configured, and the area surface average roughness (Sa) in the face where the release layer is configured ( Sa) is 7nm or less. If Sa is 7nm or less, even the release layer laminated on the surface layer A can exhibit high smoothness, and pinholes and the like are less likely to occur during molding of the ultra-thin ceramic green body laminated on the release layer. Furthermore, when the release layer is formed, protrusions of the release layer components aggregated on the surface layer A can be suppressed, and deterioration of the smoothness of the release layer surface can be prevented.
表面層A之區域表面平均粗度(Sa)以愈小愈佳,為0.1nm以上亦無妨。於一態樣中,表面層A之區域表面平均粗度(Sa)為0.1nm以上至7nm以下,例如為0.5nm以上至5nm以下、0.5nm以上至4nm以下。藉由設定為此種範圍內,可提高離型層之平滑性,可抑制所積層之超薄層陶瓷生坯之成型時產生針孔等。再者,於形成離型層之際,可抑制離型層成分凝聚於表面層A上之突起,可防止離型層表面之平滑性惡化。The average surface roughness (Sa) of the area of the surface layer A is preferably as small as possible, and may be at least 0.1 nm. In one aspect, the area average surface roughness (Sa) of the surface layer A is not less than 0.1 nm and not more than 7 nm, for example, not less than 0.5 nm and not more than 5 nm, or not less than 0.5 nm and not more than 4 nm. By setting it within such a range, the smoothness of the release layer can be improved, and pinholes and the like can be suppressed during molding of the laminated ultra-thin layer ceramic green body. Furthermore, when the release layer is formed, protrusions of the release layer components that aggregate on the surface layer A can be suppressed, and deterioration of the smoothness of the release layer surface can be prevented.
本發明中,所謂「實質上不含無機粒子」意指以螢光X射線分析來定量無機元素的情況為50ppm以下、較佳為10ppm以下、最佳為成為檢測極限以下的含量。這是由於即便未積極地於膜中添加無機粒子,仍有源自外部異物之污染成分、於原料樹脂或是膜之製造步驟中附著至生產線或裝置的污染物會混入膜中之情況之故。In the present invention, "substantially free of inorganic particles" means that the content of inorganic elements is not more than 50 ppm, preferably not more than 10 ppm, most preferably not more than the detection limit when the inorganic elements are quantified by fluorescent X-ray analysis. This is because even if inorganic particles are not actively added to the film, there are still cases where contamination components from external foreign matter, pollutants attached to the production line or equipment in the raw material resin or film manufacturing steps are mixed into the film. .
本發明之聚酯膜基材中,亦可於配置離型層之面的相反面具有表面層B。表面層B以含有粒子為佳。藉由含有粒子,於膜之滑動性以及脫除空氣容易性方面優異,可具有優異的搬送性與捲取性。尤其以含有二氧化矽粒子以及/或是碳酸鈣粒子為佳。 表面層B中所含粒子量,合計為1000 ppm至15000ppm。此時,表面層B之膜之區域表面平均粗度(Sa)為例如1nm以上至40nm以下。更佳為5nm以上至35nm以下。當二氧化矽粒子以及/或是碳酸鈣粒子之合計為1000ppm以上、Sa為1nm以上之情況,將膜捲成輥狀時,可使得空氣均勻逸散,可使得捲繞狀態良好且平面性良好。藉由此種特徴,例如製造厚度0.2μm以上至1.0μm以下之超薄層樹脂片(例如陶瓷生坯)之情況,可防止經捲取之陶瓷生坯之皺褶、位偏,可提供搬送性、捲取性、保管性優異之離型膜。 此外,當二氧化矽粒子以及/或是碳酸鈣粒子之合計為15000ppm以下、Sa為40nm以下之情況,也作為滑劑發揮機能之粒子不易產生凝聚,不會產生粗大突起(例如高度1μm以上之突起),故於超薄層樹脂片(例如陶瓷生坯)製造時,可抑制例如捲取所致針孔之發生,可提供品質穩定之樹脂片。 In the polyester film base material of this invention, you may have the surface layer B on the surface opposite to the surface in which the release layer was arrange|positioned. Surface layer B preferably contains particles. By containing particles, it is excellent in film sliding properties and ease of degassing, and can have excellent conveyance and winding properties. It is especially preferable to contain silicon dioxide particles and/or calcium carbonate particles. The amount of particles contained in the surface layer B is 1000 ppm to 15000 ppm in total. At this time, the area average surface roughness (Sa) of the film of the surface layer B is, for example, not less than 1 nm and not more than 40 nm. More preferably, it is not less than 5 nm and not more than 35 nm. When the total amount of silica particles and/or calcium carbonate particles is more than 1000ppm, and Sa is more than 1nm, when the film is rolled into a roll, the air can escape evenly, and the winding state can be good and the planarity is good . With this feature, for example, in the case of manufacturing ultra-thin resin sheets (such as ceramic green bodies) with a thickness of 0.2 μm or more to 1.0 μm or less, it is possible to prevent wrinkles and misalignment of the coiled ceramic green bodies, and to provide transportation Release film with excellent performance, rollability and storage properties. In addition, when the total content of silica particles and/or calcium carbonate particles is 15000ppm or less and Sa is 40nm or less, the particles functioning as a lubricant are less likely to aggregate and coarse protrusions (such as those with a height of 1 μm or more) will not occur. Protrusions), so when manufacturing ultra-thin layer resin sheets (such as ceramic green bodies), it can suppress the occurrence of pinholes caused by winding, for example, and provide resin sheets with stable quality.
表面層B所含粒子除了可使用二氧化矽以及/或是碳酸鈣以外,也可使用非活性無機粒子以及/或是耐熱性有機粒子等。基於透明性、成本之觀點以使用二氧化矽粒子以及/或是碳酸鈣粒子為更佳。其他可使用之無機粒子可舉出氧化鋁-二氧化矽複合氧化物粒子、羥基磷灰石粒子等。此外,作為耐熱性有機粒子可舉出交聯聚丙烯酸系粒子、交聯聚苯乙烯粒子、苯并胍胺系粒子等。當使用有二氧化矽粒子之情況,以多孔質之膠體二氧化矽為佳。當使用有碳酸鈣粒子之情況,從防止粒子脫落之觀點來看,以聚丙烯酸系高分子化合物施以表面處理之輕質碳酸鈣為佳。As the particles contained in the surface layer B, in addition to silicon dioxide and/or calcium carbonate, inert inorganic particles and/or heat-resistant organic particles may be used. From the perspective of transparency and cost, it is better to use silicon dioxide particles and/or calcium carbonate particles. Other usable inorganic particles include alumina-silicon dioxide composite oxide particles, hydroxyapatite particles, and the like. Furthermore, examples of the heat-resistant organic particles include cross-linked polyacrylic particles, cross-linked polystyrene particles, benzoguanamine-based particles, and the like. When silica particles are used, porous colloidal silica is preferred. When calcium carbonate particles are used, light calcium carbonate surface-treated with a polyacrylic acid-based polymer compound is preferable from the viewpoint of preventing the particles from falling off.
於上述表面層B所添加之粒子之平均粒徑以0.1μm以上至2.0μm以下為佳,以0.5μm以上至1.0μm以下為特佳。只要粒子之平均粒徑為0.1μm以上,離型膜之滑動性良好故較佳。此外,只要平均粒徑為2.0μm以下,可抑制表面層A之變形,可抑制陶瓷生坯之厚度不均以及針孔之發生。The average particle size of the particles added to the above-mentioned surface layer B is preferably from 0.1 μm to 2.0 μm, particularly preferably from 0.5 μm to 1.0 μm. As long as the average particle diameter of the particles is 0.1 μm or more, the sliding property of the release film is good, so it is preferable. In addition, if the average particle diameter is 2.0 μm or less, the deformation of the surface layer A can be suppressed, and the uneven thickness of the ceramic green body and the occurrence of pinholes can be suppressed.
上述表面層B亦可含有2種類以上不同素材之粒子。此外,亦可含有同種粒子但平均粒徑不同者。此外,2種類以上之不同粒子也可在上述範圍內具有不同平均粒徑。藉由含有不同的2種類粒子,可高度地抑制於表面層B所形成之凹凸,可兼顧滑動性與平滑性故較佳。The above-mentioned surface layer B may contain two or more types of particles of different materials. In addition, particles of the same kind but having different average particle diameters may be included. Moreover, different particle|grains of 2 or more types may have a different average particle diameter within the said range. By containing two different types of particles, it is possible to suppress the unevenness formed on the surface layer B to a high degree, and it is preferable because it can balance sliding properties and smoothness.
基於減少針孔之觀點,屬於設置離型層之側的層亦即表面層A為了防止混入粒子或是雜質,以不使用再生原料等為佳。From the viewpoint of reducing pinholes, it is preferable not to use recycled raw materials, etc., in order to prevent particles or impurities from being mixed into the surface layer A, which is the layer on the side where the release layer is provided.
屬於設置離型層之側的層亦即表面層A之厚度比率以基材膜之總層厚度之20%以上至50%以下為佳。只要為20%以上,不易承受到來自膜內部之表面層B等所含粒子之影響,可使得區域表面平均粗度Sa滿足上述範圍故較佳。若為基材膜之總層厚度之50%以下,可增加共擠出所得表面層B、上述中間層C中之再生原料之使用比率,環境負荷變小故較佳。The thickness ratio of the surface layer A, which is the layer on the side where the release layer is provided, is preferably 20% or more and 50% or less of the total layer thickness of the base film. As long as it is more than 20%, it is not easy to be affected by particles contained in the surface layer B inside the film, and the average surface roughness Sa of the area can satisfy the above range, so it is preferable. If it is less than 50% of the total layer thickness of the base film, the use ratio of recycled materials in the surface layer B obtained by co-extrusion and the above-mentioned intermediate layer C can be increased, and the environmental load is reduced, so it is preferable.
此外,基於經濟性之觀點,上述表面層A以外之層(表面層B或是前述中間層C)中可使用50質量%至90質量%之膜屑或寶特瓶之再生原料。此便是此種情況,表面層B所含滑劑之種類與量、粒徑以及區域表面平均粗度(Sa)以滿足上述範圍為佳。In addition, from an economic point of view, 50% to 90% by mass of film scraps or recycled plastic bottles can be used in layers other than the above-mentioned surface layer A (surface layer B or the aforementioned intermediate layer C). This is the case, and it is preferable that the type and amount of the lubricant contained in the surface layer B, the particle size, and the area surface average roughness (Sa) satisfy the above-mentioned range.
此外,基於後續塗布之離型層等之密接性之提升或是抗靜電等之考量,可於表面層A以及/或是表面層B之表面在製膜步驟內之延伸前或是單軸延伸後設置塗層,也可施以電暈處理等。於表面層A上設置塗層之情況,該塗層以實質上不含粒子為佳。In addition, based on the improvement of the adhesion of the release layer coated later or the consideration of antistatic, etc., the surface of the surface layer A and/or the surface of the surface layer B can be stretched before or uniaxially in the film forming step. After coating, corona treatment, etc. can also be applied. In the case of providing a coating on the surface layer A, it is preferable that the coating does not substantially contain particles.
(離型層) 本發明中,離型層係積層於表面層A上。本發明中,離型層係離型層形成組成物經硬化之層,離型層以及離型層形成組成物至少含有陽離子硬化型聚二甲基矽氧烷(a),離型層之區域表面粗度(Sa)為2nm以下,存在於離型層表面之高度10nm以上之突起數為200個/mm 2以下。 離型層因具有此種特徴,可抑制於要求高平滑性之超薄膜樹脂片(例如陶瓷生坯)產生針孔,可形成膜厚均勻的樹脂片。 更詳細來說,本發明之離型層可抑制氧阻礙所致硬化不良,可展現離型層之高交聯。發揮此種效果之本發明例如可提高離型層表面之耐溶劑性。藉由提高離型層表面之耐溶劑性,可抑制因著陶瓷生坯之成型時、內部電極之印刷時所使用之有機溶媒造成離型層受到侵蝕,可具有高剝離性。 此外,若為本發明,無須為了促進硬化反應而使用130℃以上之高熱。因此,可抑制加工時之熱造成離型膜之平面性受損。此外,可抑制異物混入樹脂片成型用離型膜,抑制發生離型層之傷痕,對於陶瓷生坯等被離型體可抑制異物、傷痕之轉印所致片損傷的發生。 (Release layer) In this invention, a release layer is laminated|stacked on the surface layer A. As shown in FIG. In the present invention, the release layer is a hardened layer of the release layer forming composition, the release layer and the release layer forming composition contain at least cation-hardening polydimethylsiloxane (a), and the release layer region The surface roughness (Sa) is 2nm or less, and the number of protrusions with a height of 10nm or more existing on the surface of the release layer is 200/mm 2 or less. Due to the characteristics of the release layer, it can suppress pinholes in ultra-thin film resin sheets (such as ceramic green bodies) that require high smoothness, and can form resin sheets with uniform film thickness. More specifically, the release layer of the present invention can suppress poor hardening caused by oxygen hindrance, and can exhibit high crosslinking of the release layer. This invention which exhibits such an effect can improve the solvent resistance of the release layer surface, for example. By improving the solvent resistance of the surface of the release layer, it is possible to suppress the erosion of the release layer due to the organic solvent used in the molding of the ceramic green body and the printing of the internal electrodes, and high peelability can be achieved. In addition, according to the present invention, it is not necessary to use high heat above 130° C. to accelerate the hardening reaction. Therefore, damage to the planarity of the release film due to heat during processing can be suppressed. In addition, it can prevent foreign matter from being mixed into the release film for resin sheet molding, and prevent the occurrence of scratches on the release layer. For release objects such as ceramic green bodies, it can suppress the occurrence of sheet damage caused by the transfer of foreign matter and scratches.
離型層之區域表面平均粗度(Sa)為2nm以下。此外,存在於離型層表面之高度10nm以上之突起數為200個/mm 2以下。離型膜之離型層表面為避免於離型層上所塗布、成型之陶瓷片產生缺陷,故上述區域表面平均粗度(Sa)與10nm以上之突起數滿足預定條件。 只要區域表面粗度(Sa)為2nm以下、且高度10nm以上之突起數為200個/mm 2以下,於陶瓷片成型時不會於陶瓷片產生針孔等缺點,良率良好故較佳。 更佳為,區域表面粗度(Sa)為1.7nm以下,例如亦可為1.6nm以下、1.5nm以下。於一態樣中,區域表面粗度(Sa)為1.3nm以下。此外,區域表面粗度(Sa)可為0.1nm以上,可為0.2nm以上。 另一方面,於一態樣中,高度10nm以上之突起數為180個/mm 2以下,例如為170個/mm 2以下,亦可為160個/mm 2以下。於一態樣中,高度10nm以上之突起數可為120個/mm 2以下,亦可為100個/mm 2以下。此外,高度10nm以上之突起數可為1個/mm 2以上,亦可為例如10個/mm 2以上。 藉由使得高度10nm以上之突起數為上述範圍內,於陶瓷片不會產生針孔等缺點,且可均衡地具有優異之離型性。 更佳為區域表面粗度(Sa)為1.0nm以下,且高度10nm以上之突起數為100個/mm 2以下。 具有本發明相關之區域表面平均粗度(Sa)與突起數之離型層可展現極優異之平滑性。 The area surface average roughness (Sa) of the release layer is 2nm or less. In addition, the number of protrusions with a height of 10 nm or more present on the surface of the release layer is 200/mm 2 or less. The surface of the release layer of the release film is to avoid defects in the coated and molded ceramic sheet on the release layer, so the average surface roughness (Sa) and the number of protrusions above 10nm in the above region meet the predetermined conditions. As long as the area surface roughness (Sa) is 2nm or less, and the number of protrusions with a height of 10nm or more is 200/ mm2 or less, there will be no defects such as pinholes in the ceramic sheet during molding of the ceramic sheet, and the yield rate is good, so it is better. More preferably, the area surface roughness (Sa) is 1.7 nm or less, for example, 1.6 nm or less, 1.5 nm or less. In one aspect, the area surface roughness (Sa) is 1.3 nm or less. In addition, the area surface roughness (Sa) may be not less than 0.1 nm, and may be not less than 0.2 nm. On the other hand, in one aspect, the number of protrusions with a height of 10 nm or more is 180/mm 2 or less, for example, 170/mm 2 or less, or 160/mm 2 or less. In one aspect, the number of protrusions with a height of 10 nm or more may be 120 or less, or 100/mm 2 or less. In addition, the number of protrusions with a height of 10 nm or more may be 1/mm 2 or more, for example, may be 10/mm 2 or more. By setting the number of protrusions with a height of 10 nm or more within the above-mentioned range, defects such as pinholes do not occur on the ceramic sheet, and excellent release properties can be provided in a balanced manner. More preferably, the area surface roughness (Sa) is 1.0 nm or less, and the number of protrusions with a height of 10 nm or more is 100/mm 2 or less. The release layer having the area surface average roughness (Sa) and the number of protrusions related to the present invention can exhibit extremely excellent smoothness.
於一態樣中,離型層之最大突起高度(Sp)為20nm以下。若最大突起高度為此種範圍,可進而抑制陶瓷片之缺陷。更佳為最大突起高度(Sp)為15nm以下,更佳為10nm以下。 於一態樣中,存在於離型層表面之高度5nm以上至未達10nm之突起數與前述10nm以上之突起數之合計為1500個/mm 2以下。若存在於離型層上之高度5nm以上至未達10nm之突起數與前述10nm以上之突起數之合計為1500個/mm 2以下,可進而抑制陶瓷片之缺陷,可獲得具有高平滑性之離型層故較佳。 更佳為高度5nm以上至未達10nm之突起數與前述10nm以上之突起數之合計為1000個/mm 2以下,例如以500個/mm 2以下為更佳。 In one aspect, the maximum protrusion height (Sp) of the release layer is 20 nm or less. If the maximum protrusion height is within such a range, defects of the ceramic sheet can be further suppressed. More preferably, the maximum protrusion height (Sp) is 15 nm or less, more preferably 10 nm or less. In one aspect, the sum of the number of protrusions present on the surface of the release layer with a height of 5 nm or more to less than 10 nm and the number of protrusions of 10 nm or more is 1500/mm 2 or less. If the total number of protrusions with a height of 5 nm or more to less than 10 nm on the release layer and the number of protrusions with a height of 10 nm or more is 1500/ mm2 or less, the defects of the ceramic sheet can be further suppressed, and a product with high smoothness can be obtained. The release layer is therefore better. More preferably, the sum of the number of protrusions with a height of 5 nm or more to less than 10 nm and the number of protrusions of 10 nm or more is 1000/mm 2 or less, for example, 500/mm 2 or less.
本發明之樹脂片成型用離型膜相關之離型層為離型層形成組成物經硬化之層,離型層形成組成物至少含有陽離子硬化型聚二甲基矽氧烷(a)。陽離子硬化型聚二甲基矽氧烷(a)因著陽離子硬化反應而進行交聯反應,故不會發生氧阻礙所致硬化不良,而成為耐溶劑性優異之離型層。因此,無須擔心陶瓷生坯成型時、內部電極印刷時等所使用之有機溶媒造成離型層受到侵蝕,可獲得剝離性優異之離型層。The release layer related to the release film for resin sheet molding of the present invention is a layer obtained by hardening the release layer forming composition, and the release layer forming composition contains at least cation-curable polydimethylsiloxane (a). Cationic hardening type polydimethylsiloxane (a) undergoes crosslinking reaction due to cationic hardening reaction, so it does not cause poor hardening due to oxygen inhibition, and becomes a release layer with excellent solvent resistance. Therefore, there is no need to worry about the corrosion of the release layer due to the organic solvent used in the molding of ceramic green bodies and the printing of internal electrodes, and a release layer with excellent peelability can be obtained.
進而本發明人等發現在含有陽離子硬化型聚二甲基矽氧烷(a)之離型層中,陽離子硬化型聚二甲基矽氧烷(a)之量高對於實現具有平滑性之離型層而言為重要。 陽離子硬化型聚二甲基矽氧烷(a)於離型層中含有90mg/m 2以下,例如含有60mg/m 2以下,以含有50mg/m 2以下為佳,以含有40mg/m 2以下為更佳,以含有30mg/m 2以下為更佳。此外,陽離子硬化型聚二甲基矽氧烷(a)例如亦可為20mg/m 2以下。 若離型層中之陽離子硬化型聚二甲基矽氧烷(a)之含量為50mg/m 2以下,可抑制形成離型層之步驟(例如乾燥步驟)中聚二甲基矽氧烷(a)出現凝聚,無須擔心產生多數本發明範圍外之突起,可發揮本案發明之效果。 於一態樣中,可於離型層、離型層形成組成物中含有陽離子硬化型聚二甲基矽氧烷(a)以外之成分。即便於此情況,雖不應基於特定理論作判斷,但本發明中當離型層加工時聚二甲基矽氧烷(a)可能偏析於離型層表面,若含量為50mg/m 2以下則不易凝聚,可形成具有高平滑性之離型層。 本發明相關之聚二甲基矽氧烷(a)之含量愈少愈不易凝聚,於離型層中只要為0.1mg/m 2以上即可保持離型層之均平性,可獲得塗層外觀優異、高平滑性之離型層。此外,只要為0.1mg/m 2以上在剝離性也優異故較佳。例如,聚二甲基矽氧烷(a)之含量也可為0.5mg/m 2以上。 本發明中,離型層形成組成物含有陽離子硬化型聚二甲基矽氧烷(a)。此外,於離型層形成組成物經硬化之離型層中,存在有源自陽離子硬化型聚二甲基矽氧烷(a)之化合物(硬化物)。本說明書中,有時針對離型層中所存在之源自聚二甲基矽氧烷(a)之化合物也簡稱為陽離子硬化型聚二甲基矽氧烷(a)。 Furthermore, the present inventors have found that in the release layer containing the cation-curable polydimethylsiloxane (a), a high amount of the cation-curable polydimethylsiloxane (a) is important for realizing a release layer having smoothness. Type layer is important. Cationic hardening type polydimethylsiloxane (a) contains 90 mg/ m2 or less in the release layer, for example, 60 mg/ m2 or less, preferably 50 mg/ m2 or less, preferably 40 mg/ m2 or less More preferably, it is better to contain 30mg/ m2 or less. In addition, the cation-curable polydimethylsiloxane (a) may be 20 mg/m 2 or less, for example. If the content of the cation-hardening type polydimethylsiloxane (a) in the release layer is 50 mg/m or less, it can suppress the polydimethylsiloxane (a) in the step of forming the release layer (such as the drying step). a) Agglomeration occurs, and there is no need to worry about producing a large number of protrusions outside the scope of the present invention, and the effect of the present invention can be exerted. In one aspect, components other than the cation-curable polydimethylsiloxane (a) may be contained in the release layer and the release layer forming composition. Even in this case, although it should not be judged based on a specific theory, in the present invention, when the release layer is processed, polydimethylsiloxane (a) may segregate on the surface of the release layer, if the content is 50mg/ m2 or less It is not easy to coagulate, and can form a release layer with high smoothness. The smaller the content of polydimethylsiloxane (a) related to the present invention, the less likely it is to coagulate. As long as the content of the polydimethylsiloxane (a) in the release layer is more than 0.1mg/ m2 , the uniformity of the release layer can be maintained and the coating can be obtained. A release layer with excellent appearance and high smoothness. Moreover, if it is 0.1 mg/m 2 or more, it is also excellent in detachability, and it is preferable. For example, the content of polydimethylsiloxane (a) may be 0.5 mg/m 2 or more. In the present invention, the release layer forming composition contains cation-curable polydimethylsiloxane (a). In addition, the compound (cured product) derived from the cation-curable polydimethylsiloxane (a) exists in the release layer in which the release layer forming composition was cured. In this specification, the compound derived from polydimethylsiloxane (a) present in the release layer may also be simply referred to as cation-curable polydimethylsiloxane (a).
本案發明中所謂陽離子硬化型聚二甲基矽氧烷(a)意指具有陽離子硬化性官能基之聚二甲基矽氧烷。所謂陽離子硬化性官能基可舉出顯示陽離子硬化性之反應性官能基,具體上可舉出乙烯醚基、氧雜環丁基、環氧基、脂環式環氧基為例。基於反應性之觀點,當中又以具有選自氧雜環丁基、環氧基、脂環式環氧基中至少1種之官能基為佳,以脂環式環氧基為最佳。藉由具有此種官能基,可藉由陽離子硬化反應來形成交聯結構,成為耐溶劑性優異、具有優異剝離性之離型層故較佳。The cation-curable polydimethylsiloxane (a) in the present invention refers to a polydimethylsiloxane having a cationic-curable functional group. The cation-curable functional group includes reactive functional groups exhibiting cation-curable properties, and specifically, vinyl ether groups, oxetanyl groups, epoxy groups, and alicyclic epoxy groups are examples. From the viewpoint of reactivity, among them, it is preferable to have at least one functional group selected from the group consisting of oxetanyl, epoxy, and alicyclic epoxy, and alicyclic epoxy is most preferred. By having such a functional group, a cross-linked structure can be formed by a cationic hardening reaction, and it becomes a release layer having excellent solvent resistance and excellent peelability, so it is preferable.
陽離子硬化型聚二甲基矽氧烷(a)所具有之陽離子硬化性官能基之數量只要為1個以上即可。例如,藉由具有2個以上的陽離子硬化性官能基,陽離子硬化反應變得更容易進行,成為交聯密度高的離型層故較佳。陽離子硬化性官能基之導入位置並無特別限定,一般可位於聚二甲基矽氧烷之側鎖或末端。聚二甲基矽氧烷之結構可為直鏈結構也可為分支結構,即便具有陽離子硬化性官能基以外之官能基也可無問題地使用。The number of the cation-curable functional groups which the cation-curable polydimethylsiloxane (a) has should just be 1 or more. For example, by having two or more cation-curable functional groups, the cation-curing reaction proceeds more easily, and it is preferable to form a release layer with a high crosslink density. The introduction position of the cation-curable functional group is not particularly limited, and generally can be located at the side lock or terminal of polydimethylsiloxane. The structure of polydimethylsiloxane may be a linear structure or a branched structure, and it can be used without any problem even if it has a functional group other than a cation-curable functional group.
陽離子硬化型聚二甲基矽氧烷(a)可適宜地使用市售者。舉例包括荒川化學工業公司製之矽利康利斯(註冊商標)UV POLY200、UV POLY201、UV POLY215、UV RCA200、UV RCA251、信越化學工業公司製之X-62-7622、X-62-7629、X-62-7660、KF-101、KF-105、X-22-343、X-22-169AS、X-22-169B、X-22-163、X-22-173BX、X-22-173DX、X-22-9002、Momentive Performance Materials公司製之UV9440E、UV9430等。As the cation-curing polydimethylsiloxane (a), a commercially available one can be used suitably. Examples include Silicon Corlis (registered trademark) UV POLY200, UV POLY201, UV POLY215, UV RCA200, UV RCA251 manufactured by Arakawa Chemical Industry Co., Ltd., X-62-7622, X-62-7629, X -62-7660, KF-101, KF-105, X-22-343, X-22-169AS, X-22-169B, X-22-163, X-22-173BX, X-22-173DX, X -22-9002, UV9440E, UV9430, etc. manufactured by Momentive Performance Materials.
陽離子硬化型聚二甲基矽氧烷(a)之重量平均分子量以1000至500000為佳,以5000至100000為更佳。若重量平均分子量為1000以上,陽離子硬化反應容易進行而剝離性優異故較佳。若為500000以下則黏度不會變得過高,成為塗敷性優異、具有高平面性之離型層故較佳。The weight average molecular weight of the cation-curable polydimethylsiloxane (a) is preferably from 1,000 to 500,000, more preferably from 5,000 to 100,000. When the weight average molecular weight is 1000 or more, the cationic hardening reaction is easy to proceed and the releasability is excellent, so it is preferable. If it is 500,000 or less, the viscosity does not become too high, and it is excellent in applicability and has a high planarity release layer, so it is preferable.
本發明之離型層形成組成物中除了含有陽離子硬化型聚二甲基矽氧烷(a)也可含有其他樹脂。此情況可使得離型層之膜厚薄化。本發明中由於在實質不含無機粒子之基材膜的表面層A上設置離型層,故即便離型層之膜厚薄,也可成為具有極高平滑性之離型層。此外,由於離型層之膜厚薄,故硬化反應容易進行,能以更高速進行加工,可高經濟性地獲得離型層。The release layer-forming composition of the present invention may contain other resins in addition to the cation-curable polydimethylsiloxane (a). In this case, the film thickness of the release layer can be reduced. In the present invention, since the release layer is provided on the surface layer A of the substrate film substantially not containing inorganic particles, even if the film thickness of the release layer is thin, it can be a release layer with extremely high smoothness. In addition, since the film thickness of the release layer is thin, the hardening reaction is easy to proceed, and processing can be performed at a higher speed, and the release layer can be obtained with high economical efficiency.
若膜厚進而薄化,無須擔心於離型加工步驟等所存在之極微小異物等夾帶至離型層中。因此,於離型層表面無產生源自異物之突起之虞,可獲得前述般具有平滑表面之離型層。If the film thickness is further reduced, there is no need to worry about the tiny foreign matter that exists in the release processing steps and the like being entrained into the release layer. Therefore, there is no risk of protrusions originating from foreign matter on the surface of the release layer, and a release layer having a smooth surface as described above can be obtained.
以陽離子硬化型聚二甲基矽氧烷(a)為主成分之組成物經硬化之離型層之情況,離型層之膜厚以0.001μm以上至未達0.050μm為佳。若為0.001μm以上由於離型性優異故較佳。若為未達0.050μm可防止離型層形成組成物之凝聚,成為平滑之離型層故較佳。 此外,本發明中,以陽離子硬化型聚二甲基矽氧烷(a)為主成分之情況,相對於離型層之樹脂固形物100質量份,組成物含有陽離子硬化型聚二甲基矽氧烷(a)50質量份以上,例如超過50質量份,較佳為70質量份以上,例如含有80質量份以上,於一態樣中含有90質量份以上。此外,亦可為實質上於離型層之樹脂固形物整體含有陽離子硬化型聚二甲基矽氧烷(a)之態樣。 In the case of a hardened release layer composed of a cation-curable polydimethylsiloxane (a) as the main component, the film thickness of the release layer is preferably 0.001 μm or more and less than 0.050 μm. If it is 0.001 μm or more, it is preferable because the release property is excellent. If it is less than 0.050 μm, it is preferable to prevent the aggregation of the release layer-forming composition and form a smooth release layer. In addition, in the present invention, when the main component is cation-curable polydimethylsiloxane (a), the composition contains cation-curable polydimethylsiloxane relative to 100 parts by mass of resin solids in the release layer. The oxane (a) is 50 parts by mass or more, for example more than 50 parts by mass, preferably more than 70 parts by mass, for example 80 parts by mass or more, and in one embodiment 90 parts by mass or more. In addition, it may be an aspect in which the cation-hardening type polydimethylsiloxane (a) is contained substantially in the solid resin content of the release layer as a whole.
本發明之離型層形成組成物中除了含有陽離子硬化型聚二甲基矽氧烷(a)亦可含有陽離子硬化型樹脂(b)。此時(b)為有別於(a)之樹脂,樹脂(b)為不具聚二甲基矽氧烷結構之樹脂。具體而言,可大致分為不具聚矽氧骨架之陽離子硬化型化合物(b-1)以及具脂環式環氧基之環狀矽氧烷化合物(b-2)這2種類。The release layer forming composition of the present invention may contain a cation-curable resin (b) in addition to the cation-curable polydimethylsiloxane (a). At this time, (b) is a resin different from (a), and resin (b) is a resin without polydimethylsiloxane structure. Specifically, it can be roughly divided into two types: a cation-curable compound (b-1) not having a polysiloxane skeleton and a cyclosiloxane compound (b-2) having an alicyclic epoxy group.
於一態樣中,離型層形成組成物除了含有陽離子硬化型聚二甲基矽氧烷(a),進而含有不具聚矽氧骨架之陽離子硬化型化合物(b-1)。作為不具聚矽氧骨架之陽離子硬化型化合物(b-1)之例可舉出分子內具有2個以上陽離子硬化性官能基且不具聚矽氧骨架之聚合物、單體。當中又以具有2個以上之環氧基或是脂環式環氧基之樹脂為佳,具有2個以上之脂環式環氧基之樹脂為更佳。例如,脂環式環氧基之數量可為6個以下。 藉由具有2個以上脂環式環氧基,可藉由陽離子硬化反應而進行交聯反應,成為耐溶劑性優異之離型層。此外,同時也和離型層所含聚二甲基矽氧烷(a)進行交聯反應,故剝離性優異,且聚二甲基矽氧烷(a)朝陶瓷生坯之移動受到抑制故較佳。 In one aspect, the release layer forming composition further contains a cation-curable compound (b-1) not having a polysiloxane skeleton in addition to the cation-curable polydimethylsiloxane (a). Examples of the cation-curable compound (b-1) not having a silicone skeleton include polymers and monomers that have two or more cationic-curable functional groups in the molecule and do not have a silicone skeleton. Among them, a resin having two or more epoxy groups or alicyclic epoxy groups is preferable, and a resin having two or more alicyclic epoxy groups is more preferable. For example, the number of alicyclic epoxy groups may be 6 or less. By having 2 or more alicyclic epoxy groups, a crosslinking reaction can progress by cationic hardening reaction, and it can become the release layer excellent in solvent resistance. In addition, it also undergoes a cross-linking reaction with polydimethylsiloxane (a) contained in the release layer, so the release property is excellent, and the migration of polydimethylsiloxane (a) to the ceramic green body is suppressed. better.
於一態樣中,離型層形成組成物同時含有不具聚矽氧骨架之陽離子硬化性樹脂(b-1)與聚二甲基矽氧烷(a),故可實現具有高平滑性之離型層。藉由製成含有化合物(b-1)之離型層,可填埋於基材膜所存在之微細凹凸或極微小異物、源自寡聚物之突起等,成為超平滑的離型層。此外,由於藉由紫外線來進行硬化反應,而成為具有高平滑性之離型層。雖不應限定於特定理論來解釋,但可推測於離型層加工時之離型層形成組成物中的乾燥步驟中,均勻地使得不具聚矽氧骨架之陽離子硬化性樹脂(b-1)與聚二甲基矽氧烷(a)均平,於提升了平面性之後再進行硬化,可獲得具有高平滑性之離型層。此外,同時所含之聚二甲基矽氧烷(a)在本發明中由於在乾燥步驟中偏析於離型層表面,而可獲得剝離性也優異之離型層。In one aspect, the composition for forming the release layer contains both a cation-curable resin (b-1) without a polysiloxane skeleton and polydimethylsiloxane (a), so that a release layer with high smoothness can be realized. type layer. By making the release layer containing the compound (b-1), it is possible to fill in the fine asperities, extremely small foreign matters, protrusions derived from oligomers, etc. existing in the substrate film, and become an ultra-smooth release layer. In addition, since the hardening reaction is carried out by ultraviolet rays, it becomes a release layer with high smoothness. Although the explanation should not be limited to a specific theory, it can be speculated that in the drying step of the release layer forming composition during the release layer processing, the cation-curable resin (b-1) without the polysiloxane skeleton is uniformly made It is equal to polydimethylsiloxane (a), and then hardened after improving the planarity, a release layer with high smoothness can be obtained. In addition, since the polydimethylsiloxane (a) contained at the same time is segregated on the surface of the release layer in the drying step in the present invention, a release layer having excellent releasability can be obtained.
不具聚矽氧骨架之陽離子硬化型化合物(b-1)以低分子量之單體為佳。具體而言,數量平均分子量以200以上至未達5000為佳,以200以上至未達2500為更佳,以200以上至未達1000為更佳。若數量平均分子量為200以上,沸點不會變低,於離型層加工時之離型層形成組成物的乾燥步驟中,陽離子硬化型化合物(b-1)無揮發之虞故較佳。若未達5000,離型層之交聯密度高,耐溶劑性優異故較佳。此外,由於在乾燥步驟中能以具流動性之液狀狀態來存在,故均平性優異,成為超平滑的離型層故較佳。The cation-curable compound (b-1) not having a polysiloxane skeleton is preferably a low-molecular-weight monomer. Specifically, the number average molecular weight is preferably from 200 to less than 5,000, more preferably from 200 to less than 2,500, and more preferably from 200 to less than 1,000. If the number average molecular weight is 200 or more, the boiling point will not be lowered, and the cation-curable compound (b-1) is preferable because there is no risk of volatilization in the drying step of the release layer forming composition during release layer processing. If it is less than 5000, the crosslinking density of the release layer is high and the solvent resistance is excellent, so it is better. In addition, since it can exist in a liquid state with fluidity in the drying step, it is excellent in leveling property and is preferable as an ultra-smooth release layer.
不具聚矽氧骨架之陽離子硬化型化合物(b-1)可適宜使用市售者。作為具脂環式環氧基之化合物之例可舉出Daicel公司製之Celloxide 2021P、Celloxide 2081、Epolead GT401、EHPE3150、四國化成公司製之HiREM-1、ENEOS公司製之THI-DE、DE-102、DE-103等。作為具有環氧基之樹脂之例可舉出DIC公司之EPICLON(註冊商標)830、 840、850、1051-75M、N-665、N-670、N-690、N-673-80M、N-690-75M、Nagasechemtex公司製之Denacol(註冊商標)EX-611、EX-313、EX-321等。As the cation-curable compound (b-1) not having a silicone skeleton, commercially available ones can be used suitably. Examples of compounds having an alicyclic epoxy group include Celloxide 2021P, Celloxide 2081, Epolead GT401, EHPE3150 manufactured by Daicel, HiREM-1 manufactured by Shikoku Kasei Co., Ltd., THI-DE, DE- 102, DE-103, etc. Examples of resins having epoxy groups include EPICLON (registered trademark) 830, 840, 850, 1051-75M, N-665, N-670, N-690, N-673-80M, N- 690-75M, Denacol (registered trademark) EX-611, EX-313, EX-321 etc. manufactured by Nagasechemtex Co., Ltd.
相對於離型層中之陽離子硬化型聚二甲基矽氧烷(a)與陽離子硬化型化合物(b-1)之合計100質量份,不具聚矽氧骨架之陽離子硬化型化合物(b-1)之含量以80質量%以上為佳,以85質量%以上為更佳,以90質量%以上為甚佳。 若將陽離子硬化型化合物(b-1)之含量設為80質量%以上並成為離型層中之主成分,則成為交聯密度高且剝離性優異之離型層故較佳。此外,可減少離型層中所含陽離子硬化型聚二甲基矽氧烷(a)之含量,可抑制於乾燥步驟中源自聚二甲基矽氧烷(a)之組成凝聚於離型層表面,無平面性惡化之虞故較佳。雖陽離子硬化型化合物(b-1)之含量愈多則愈能成為平滑性優異之離型層,但為了含有陽離子硬化型聚二甲基矽氧烷(a)來確保剝離性,陽離子硬化型化合物(b-1)以99.9質量%以下為佳。 本發明中,離型層形成組成物經硬化之離型層中,存在有源自不具聚矽氧骨架之陽離子硬化型化合物(b-1)的化合物(硬化物)。本說明書中,有時候針對離型層中所存在之源自(b-1)之化合物也簡單稱為不具聚矽氧骨架之陽離子硬化型化合物(b-1)。 The cation-curable compound (b-1) not having a polysiloxane skeleton relative to 100 parts by mass of the total of the cation-curable polydimethylsiloxane (a) and the cation-curable compound (b-1) in the release layer ) content is preferably at least 80% by mass, more preferably at least 85% by mass, and most preferably at least 90% by mass. When the content of the cation-curable compound (b-1) is 80% by mass or more and it becomes the main component in the release layer, it is preferable because the release layer has a high crosslink density and is excellent in releasability. In addition, the content of cation-hardening polydimethylsiloxane (a) contained in the release layer can be reduced, and the composition derived from polydimethylsiloxane (a) can be inhibited from agglomerating on the release layer during the drying step. The surface of the layer is preferable because there is no risk of deterioration of planarity. The more the content of the cation-curing compound (b-1), the more smooth the release layer can be. However, in order to ensure the peelability by containing the cation-curing polydimethylsiloxane (a), the cation-curing type Compound (b-1) is preferably at most 99.9% by mass. In the present invention, a compound (cured product) derived from a cation-curable compound (b-1) not having a polysiloxane skeleton exists in the release layer in which the release layer-forming composition is cured. In this specification, the compound derived from (b-1) present in the release layer may also be simply referred to as a cation-curable compound (b-1) not having a polysiloxane skeleton.
當離型層形成組成物含有陽離子硬化型聚二甲基矽氧烷(a)與陽離子硬化型化合物(b-1)之情況,由於離型層之交聯密度高,耐溶劑性優異,成為具有優異之剝離力的離型層故較佳。此外,若含有陽離子硬化型化合物(b-1),由於可一邊將陽離子硬化型聚二甲基矽氧烷(a)之含量控制在預定範圍、一邊增厚離型層之膜厚故較佳。藉由增厚離型層之膜厚,可填埋基材膜所存在之傷痕、極微小凹凸,如前述般可獲得平滑的離型層故較佳。When the release layer forming composition contains cation-curable polydimethylsiloxane (a) and cation-curable compound (b-1), since the release layer has a high crosslink density and excellent solvent resistance, it becomes A release layer having excellent peeling force is therefore preferable. In addition, if the cation-curable compound (b-1) is contained, it is preferable because the film thickness of the release layer can be increased while controlling the content of the cation-curable polydimethylsiloxane (a) within a predetermined range. . By increasing the film thickness of the release layer, it is preferable to fill the flaws and extremely small unevenness of the substrate film, and obtain a smooth release layer as described above.
當離型層形成組成物含有陽離子硬化型聚二甲基矽氧烷(a)與陽離子硬化型化合物(b-1)之情況,離型層之膜厚以0.05μm以上至1.0μm以下為佳,以0.1μm以上至0.5μm以下為更佳。若為0.05μm以上,會成為平滑的離型層故較佳。若為1.0μm以下,不會發生翹曲而可獲得平面性優異之離型膜故較佳。When the release layer forming composition contains cation-curing polydimethylsiloxane (a) and cation-curing compound (b-1), the film thickness of the release layer is preferably 0.05 μm or more and 1.0 μm or less , more preferably 0.1 μm or more and 0.5 μm or less. If it is 0.05 micrometer or more, it will become a smooth release layer, so it is preferable. If it is 1.0 μm or less, it is preferable to obtain a release film having excellent planarity without warping.
於一態樣中,離型層形成組成物亦可進而包括具脂環式環氧基之環狀矽氧烷化合物(b-2)。作為具脂環式環氧基之環狀矽氧烷化合物(b-2)之例可舉出下述結構式(化學式1)所示之物等(化學式1中,R 2為碳數1至4之烷基)。此外,具環狀矽氧烷骨架之陽離子硬化型化合物(b-2)以至少具有2個以上的脂環式環氧基為佳。若脂環式環氧基為2個以上,會進行陽離子硬化反應,成為交聯密度高的離型層故較佳。 In one aspect, the release layer forming composition may further include a cyclosiloxane compound (b-2) having an alicyclic epoxy group. Examples of cyclic siloxane compounds (b-2) with alicyclic epoxy groups include those shown in the following structural formula (chemical formula 1) (in chemical formula 1, R 2 is carbon number 1 to 4 alkyl). In addition, the cation-curable compound (b-2) having a cyclic siloxane skeleton preferably has at least two or more alicyclic epoxy groups. When there are two or more alicyclic epoxy groups, the cationic hardening reaction proceeds and it becomes a release layer with a high crosslink density, so it is preferable.
[化學式1]
藉由使用具脂環式環氧基之環狀矽氧烷化合物(b-2),基於與使用前述陽離子硬化型化合物(b-1)之時同樣的理由,會成為超平滑的離型層故較佳。亦即,可填埋於基材膜所存在之微細凹凸、極微小異物、源自寡聚物之突起等。此外,由於藉由紫外線進行硬化反應,在離型層加工時之離型層形成組成物之乾燥步驟中可均勻地使得化合物(b-2)以及聚二甲基矽氧烷(a)均平,而在提升了平面性之後進行硬化,而可獲得超平滑的離型層。再者,本發明中由於同時所含之聚二甲基矽氧烷(a)在乾燥步驟中會偏析於離型層表面,而可獲得剝離性也優異之離型層。By using the cyclosiloxane compound (b-2) having an alicyclic epoxy group, an ultra-smooth release layer can be obtained for the same reason as when using the aforementioned cation-curing compound (b-1). So better. That is, it is possible to fill in fine unevenness, extremely small foreign matter, protrusions derived from oligomers, etc. present in the base film. In addition, since the hardening reaction is carried out by ultraviolet rays, the compound (b-2) and polydimethylsiloxane (a) can be uniformly averaged in the drying step of the release layer forming composition during the release layer processing. , and after hardening after improving the planarity, an ultra-smooth release layer can be obtained. Furthermore, in the present invention, since the polydimethylsiloxane (a) contained at the same time is segregated on the surface of the release layer during the drying step, a release layer having excellent peelability can be obtained.
具脂環式環氧基之環狀矽氧烷化合物(b-2)由於與陽離子硬化型聚二甲基矽氧烷(a)之互溶性良好,故於離型層中會適度地相混,彼此進行交聯反應。因此耐溶劑性優異,成為顯示優異剝離性之離型層故較佳。此外,環狀矽氧烷化合物(b-2)由於具有環狀矽氧烷結構故具有剛直的分子骨架,硬化時之膜硬度高故較佳。藉由提高膜硬度,則於剝離樹脂片(例如陶瓷生坯)之際,離型層變得不易變形,可顯示良好的剝離性。再者,離型層變得不易發生傷痕,不用擔心離型層之傷痕轉印到樹脂片(例如陶瓷生坯)而發生不良情況故較佳。Cyclic siloxane compound (b-2) with alicyclic epoxy group has good miscibility with cationic hardening polydimethylsiloxane (a), so it will be moderately mixed in the release layer , carry out cross-linking reaction with each other. Therefore, it is excellent in solvent resistance, and it is preferable since it becomes a release layer which shows excellent releasability. In addition, the cyclic siloxane compound (b-2) is preferable because it has a rigid molecular skeleton due to its cyclic siloxane structure, and has a high film hardness when cured. By increasing the film hardness, when the resin sheet (for example, a ceramic green sheet) is peeled off, the release layer becomes less likely to be deformed, and good peelability can be exhibited. Furthermore, the release layer becomes less likely to be scratched, and it is preferable that there is no fear of transfer of scratches on the release layer to a resin sheet (such as a ceramic green body).
若離型層形成組成物含有環狀矽氧烷化合物(b-2),可提高離型層對於基材膜之密接性故較佳。若離型層之密接性提升,可抑制於搬送步驟發生傷痕,此外於樹脂片剝離時不用擔心離型層轉印故較佳。When the release layer forming composition contains a cyclic siloxane compound (b-2), it is preferable because the adhesiveness of the release layer to the substrate film can be improved. If the adhesiveness of the release layer is improved, it is possible to suppress the occurrence of scratches in the conveying step, and it is preferable to avoid worrying about transfer of the release layer when the resin sheet is peeled off.
於一態樣中,環狀矽氧烷化合物(b-2)於分子內具有2個以上之脂環式環氧基。若使得分子內具有2個以上之脂環式環氧基,可藉由陽離子硬化反應來進行交聯反應,成為耐溶劑性優異之離型層。此外,同時也和離型層所含之聚二甲基矽氧烷(a)進行交聯反應,故剝離性優異,且可抑制聚二甲基矽氧烷(a)移動至陶瓷生坯故較佳。 例如,環狀矽氧烷化合物(b-2)於分子內具有6個以下之脂環式環氧基。 In one aspect, the cyclic siloxane compound (b-2) has two or more alicyclic epoxy groups in the molecule. If there are two or more alicyclic epoxy groups in the molecule, the cross-linking reaction can be carried out by cationic hardening reaction, and it becomes a release layer with excellent solvent resistance. In addition, it also undergoes a cross-linking reaction with the polydimethylsiloxane (a) contained in the release layer, so the release property is excellent, and it can inhibit the migration of the polydimethylsiloxane (a) to the ceramic green body. better. For example, the cyclic siloxane compound (b-2) has 6 or less alicyclic epoxy groups in the molecule.
具脂環式環氧基之環狀矽氧烷化合物(b-2)可使用市售者。例如,可舉出信越化學工業公司製之X-40-2670、X-40-2678等。As the cyclosiloxane compound (b-2) having an alicyclic epoxy group, a commercially available one can be used. For example, Shin-Etsu Chemical Co., Ltd. X-40-2670, X-40-2678, etc. are mentioned.
相對於離型層中之陽離子硬化型聚二甲基矽氧烷(a)與環狀矽氧烷化合物(b-2)之合計100質量份,環狀矽氧烷化合物(b-2)之含量以80質量%以上為佳,以85質量%以上為更佳,以90質量%以上為甚佳。若將環狀矽氧烷化合物(b-2)之含量設為80質量%以上並成為離型層中之主成分,則成為交聯密度高且剝離性優異之離型層故較佳。此外,可減少離型層中所含陽離子硬化型聚二甲基矽氧烷(a)之含量,於本發明中,可抑制於乾燥步驟中陽離子硬化型聚二甲基矽氧烷(a)凝聚於離型層表面,不用擔心平面性惡化故較佳。環狀矽氧烷化合物(b-2)之含量愈多則成為平滑性愈優異之離型層,例如,為了含有陽離子硬化型聚二甲基矽氧烷(a)而確保剝離性,環狀矽氧烷化合物(b-2)以99.9質量%以下為佳。 本發明中,離型層形成組成物經硬化之離型層中存在有源自環狀矽氧烷化合物(b-2)之化合物(硬化物)。本說明書中有時候將離型層中所存在之源自環狀矽氧烷化合物(b-2)之化合物簡單記載為環狀矽氧烷化合物(b-2)。 With respect to 100 parts by mass of the total of cation-curing polydimethylsiloxane (a) and cyclic siloxane compound (b-2) in the release layer, the amount of cyclic siloxane compound (b-2) The content is preferably at least 80% by mass, more preferably at least 85% by mass, and even more preferably at least 90% by mass. When the content of the cyclic siloxane compound (b-2) is 80% by mass or more and it becomes the main component in the release layer, it is preferable because the release layer has a high crosslink density and is excellent in releasability. In addition, the content of the cation-curable polydimethylsiloxane (a) contained in the release layer can be reduced, and in the present invention, the cation-curable polydimethylsiloxane (a) in the drying step can be suppressed It is better to condense on the surface of the release layer without worrying about deterioration of planarity. The more the content of the cyclic siloxane compound (b-2), the better the smoothness of the release layer. For example, in order to ensure the peelability by containing the cation-curing polydimethylsiloxane (a), the cyclic The siloxane compound (b-2) is preferably at most 99.9% by mass. In the present invention, the compound (cured product) derived from the cyclic siloxane compound (b-2) exists in the release layer in which the release layer forming composition is cured. In this specification, the compound derived from the cyclic siloxane compound (b-2) which exists in a release layer may be simply described as a cyclic siloxane compound (b-2).
當離型層形成組成物含有陽離子硬化型聚二甲基矽氧烷(a)與環狀矽氧烷化型化合物(b-2)之情況,離型層之膜厚以0.05μm以上至1.0μm以下為佳,以0.1μm以上至0.5μm以下為更佳。若為0.05μm以上,由於成為平滑的離型層故較佳。若為1.0μm以下,可避免發生翹曲而獲得平面性優異之離型膜故較佳。When the release layer forming composition contains cationic hardening type polydimethylsiloxane (a) and cyclic siloxane type compound (b-2), the film thickness of the release layer is 0.05 μm or more to 1.0 μm It is preferably not more than μm, more preferably not less than 0.1 μm and not more than 0.5 μm. If it is 0.05 micrometer or more, since it becomes a smooth release layer, it is preferable. If it is 1.0 μm or less, warping can be avoided and a release film with excellent planarity can be obtained, so it is preferable.
於一態樣中,離型層可同時包含陽離子硬化型樹脂(b-1)與環狀矽氧烷化合物(b-2),這些陽離子硬化型樹脂(b-1)與環狀矽氧烷化合物(b-2)之合計量相對於離型層中之陽離子硬化型聚二甲基矽氧烷(a)與陽離子硬化型化合物(b-1)與環狀矽氧烷化合物(b-2)之合計100質量份,可為80質量%以上至99.9質量%以下。In one aspect, the release layer may contain both cation-curing resin (b-1) and cyclic siloxane compound (b-2), and these cation-curing resin (b-1) and cyclic siloxane The total amount of compound (b-2) relative to the cation-curing polydimethylsiloxane (a), cation-curing compound (b-1) and cyclic siloxane compound (b-2) in the release layer ) in a total of 100 parts by mass may be more than 80% by mass and less than or equal to 99.9% by mass.
本發明中,為了形成離型層必須進行陽離子硬化反應。因此,離型層形成組成物以含有酸產生劑(c)為佳。此外,離型層可存在源自酸產生劑(c)之化合物。此處,針對離型層中所存在之源自酸產生劑(c)之化合物有時也簡稱為酸產生劑(c)。 酸產生劑並無特別限定可使用一般的酸產生劑,但藉由使用在紫外線照射下會產生酸的光酸產生劑,可抑制加工時之熱量,成為平面性優異之離型層故較佳。 In the present invention, it is necessary to carry out a cation hardening reaction in order to form a release layer. Therefore, it is preferable that the composition for forming a release layer contains an acid generator (c). In addition, a compound derived from an acid generator (c) may exist in the release layer. Here, the compound derived from the acid generator (c) present in the release layer may also be simply referred to as the acid generator (c). The acid generator is not particularly limited. General acid generators can be used, but by using a photoacid generator that generates acid under ultraviolet radiation, heat during processing can be suppressed, and it is preferable to form a release layer with excellent planarity. .
基於反應性之觀點,光酸產生劑以使用由鎓離子與非親核性陰離子所成之鹽為適宜。此外,也可使用以鐵芳烴錯合物為代表之有機金屬錯合物、以鋽為代表之碳陽離子鹽,也可使用以蔥衍生物或吸電子基所取代之酚類,例如五氟苯酚。From the viewpoint of reactivity, it is preferable to use a salt of an onium ion and a non-nucleophilic anion as a photoacid generator. In addition, organometallic complexes represented by iron arene complexes, carbocation salts represented by arborium, and phenols substituted with onion derivatives or electron-withdrawing groups, such as pentafluorophenol, can also be used. .
當使用由前述鎓離子與非親核性陰離子所成之鹽作為光酸產生劑之情況,鎓離子可使用例如錪鎓、鋶、銨。作為鎓離子之有機基可使用三芳基、二芳基(單烷基)、單芳基(二烷基)、三烷基,也可導入二苯甲酮、9-芴,可使用其他的有機基。非親核性陰離子以使用六氟磷酸鹽、六氟銻酸鹽、六氟硼酸鹽、四(五氟苯基)硼酸鹽為適宜。此外,也可使用四(五氟苯基)鎵離子、將數個氟陰離子取代於全氟烷基或有機基之陰離子,也可使用其他的陰離子成分。When using a salt formed of the aforementioned onium ion and a non-nucleophilic anion as the photoacid generator, the onium ion can be, for example, iodonium, perium, or ammonium. As the organic group of the onium ion, triaryl, diaryl (monoalkyl), monoaryl (dialkyl), and trialkyl can be used, and benzophenone and 9-fluorene can also be introduced, and other organic groups can be used. base. As the non-nucleophilic anion, hexafluorophosphate, hexafluoroantimonate, hexafluoroborate, and tetrakis(pentafluorophenyl)borate are preferably used. In addition, tetrakis(pentafluorophenyl)gallium ions, anions obtained by substituting several fluorine anions for perfluoroalkyl groups or organic groups, or other anion components may also be used.
光酸產生劑之添加量相對於離型層中之陽離子硬化型聚二甲基矽氧烷(a)與陽離子硬化型化合物(b-1)以及/或是環狀矽氧烷化合物(b-2)之合計100質量份為0.1質量%至10質量%,更佳為0.5質量%至8質量%。更佳為1質量%至5質量%。若為0.1質量%以上,無須擔心所產生之酸量變得不充分而成為硬化不足故較佳。此外,若為10質量%以下,所產生之酸量成為適量,可抑制酸往所成型之陶瓷生坯的移動量故較佳。The amount of the photoacid generator added is relative to the cation-curing polydimethylsiloxane (a) and the cation-curing compound (b-1) and/or the cyclic siloxane compound (b-1) in the release layer. 2) The total 100 mass parts is 0.1 mass % - 10 mass %, More preferably, it is 0.5 mass % - 8 mass %. More preferably, it is 1 mass % to 5 mass %. If it is 0.1% by mass or more, there is no need to worry about insufficient hardening due to an insufficient amount of generated acid. In addition, if it is 10% by mass or less, the amount of generated acid becomes appropriate, and the amount of migration of acid to the molded ceramic green body can be suppressed, so it is preferable.
本說明書中,所謂離型層中之陽離子硬化型聚二甲基矽氧烷(a)與陽離子硬化型化合物(b-1)以及/或是環狀矽氧烷化合物(b-2)之合計100質量份,意指陽離子硬化型聚二甲基矽氧烷(a)之固形物、陽離子硬化型樹脂(b)之固形物之合計值。此外,在離型層不含陽離子硬化型樹脂(b)之態樣中,陽離子硬化型聚二甲基矽氧烷(a)之重量相當於離型層中之樹脂固形物100質量份。In this specification, the sum of cation-curing polydimethylsiloxane (a) and cation-curing compound (b-1) and/or cyclic siloxane compound (b-2) in the release layer 100 parts by mass means the total value of the solid content of cation-curable polydimethylsiloxane (a) and the solid content of cation-curable resin (b). In addition, in the form where the release layer does not contain the cation-curable resin (b), the weight of the cation-curable polydimethylsiloxane (a) corresponds to 100 parts by mass of the resin solids in the release layer.
於一態樣中,離型層形成組成物包含SP值(δ)為14以上至17以下之有機溶媒,離型層形成組成物係使得SP值(δ)為14以上至17以下之前述有機溶媒相對於離型層形成組成物之總重量100質量份以10質量%以上之量含有。 SP值(δ)為14至17之有機溶媒對於陽離子硬化型聚二甲基矽氧烷(a)展現優異之溶解性。因此,於塗布步驟後之乾燥步驟中,即便有機溶媒乾燥而提高了離型層形成組成物中之陽離子硬化型聚二甲基矽氧烷(a)的濃度仍可保持在均勻溶解之狀態,不會凝聚而良好地均平,可獲得平滑的離型層。 此外,只要含量為10質量%以上,由於在乾燥中,陽離子硬化型聚二甲基矽氧烷(a)可保持長時間呈現溶解之狀態,故不用擔心乾燥中出現凝聚造成平滑性惡化故較佳。 SP值(δ)為14以上至17以下之前述有機溶媒之詳細將於後述。 In one aspect, the release layer-forming composition includes an organic solvent with an SP value (δ) of 14 to 17, and the release layer-forming composition is such that the SP value (δ) is 14 to 17. The solvent is contained in an amount of 10% by mass or more with respect to 100 parts by mass of the total weight of the release layer forming composition. An organic solvent having an SP value (δ) of 14 to 17 exhibits excellent solubility for the cation-curing polydimethylsiloxane (a). Therefore, in the drying step after the coating step, even if the organic solvent is dried to increase the concentration of the cation-curable polydimethylsiloxane (a) in the release layer forming composition, it can still be maintained in a uniformly dissolved state, It can be well averaged without agglomeration, and a smooth release layer can be obtained. In addition, as long as the content is 10% by mass or more, the cation-curable polydimethylsiloxane (a) can remain in a dissolved state for a long time during drying, so there is no need to worry about deterioration of smoothness caused by aggregation during drying. good. Details of the aforementioned organic solvent having an SP value (δ) of 14 or more and 17 or less will be described later.
本發明中,只要在不阻礙本發明之效果的範圍內,亦可於離型層添加密接提升劑、抗靜電劑等添加劑等。此外,為了提高相對於基材之密接性,在設置離型塗布層之前於聚酯膜表面施以錨固塗布、電暈處理、電漿處理、大氣壓電漿處理等之前處理亦較佳。In the present invention, additives such as adhesion improving agents and antistatic agents may be added to the release layer as long as the effects of the present invention are not hindered. In addition, in order to improve the adhesion to the base material, it is also preferable to apply anchor coating, corona treatment, plasma treatment, atmospheric pressure plasma treatment, etc. to the surface of the polyester film before providing the release coating layer.
利用本發明所獲得之離型膜將陶瓷生坯加以剝離時的剝離力以0.01mN/mm以上至2.0mN/mm以下為佳。更佳為0.05mN/mm以上至1.0mN/mm以下。若剝離力為0.01mN/mm以上,不用擔心搬運時陶瓷生坯隆起故較佳。若剝離力為2.0mN/mm以下,不用擔心剝離時陶瓷生坯受損故較佳。When the release film obtained by the present invention is used to peel off the ceramic green body, the peeling force is preferably not less than 0.01 mN/mm and not more than 2.0 mN/mm. More preferably, it is 0.05 mN/mm or more and 1.0 mN/mm or less. If the peeling force is 0.01 mN/mm or more, it is preferable because there is no fear of the ceramic green body rising during transportation. If the peeling force is 2.0 mN/mm or less, there is no need to worry about damage to the green ceramic body during peeling.
藉由本發明所得到的離型膜由於使用了高度平坦化之基材膜,故即便離型層之厚度為1.0μm以下、甚至是0.5μm以下、甚至是0.3μm以下,仍可使得離型層表面平滑化。因此,可減少所使用之溶劑量、樹脂量而對環境良好,可廉價地製作出超薄層陶瓷生坯成型用之離型膜。The release film obtained by the present invention uses a highly planarized base film, so even if the thickness of the release layer is less than 1.0 μm, or even less than 0.5 μm, or even less than 0.3 μm, the release layer can still be made Surface smoothing. Therefore, the amount of solvent and resin used can be reduced, which is environmentally friendly, and a release film for ultra-thin ceramic green body molding can be produced at low cost.
(離型膜之製造方法) 本發明之其他實施態樣中提供一種樹脂片成型用離型膜之製造方法,具有以下步驟。 塗布步驟,係於具有表面層A之聚酯膜之前述表面層A上塗布離型層形成組成物,前述表面層A為實質上不含無機粒子之層,離型層形成組成物含有陽離子硬化型聚二甲基矽氧烷(a);乾燥步驟,係將塗布有離型層形成組成物之前述聚酯膜加以加熱乾燥,前述加熱乾燥具有第1乾燥步驟以及接續之第2乾燥步驟,前述第1乾燥步驟中之乾燥溫度T1高於前述第2乾燥步驟中之乾燥溫度T2;以及,光硬化步驟,係於前述乾燥步驟後照射活性能量線,使得離型層形成組成物硬化。 (Manufacturing method of release film) Another embodiment of the present invention provides a method for manufacturing a release film for forming a resin sheet, which includes the following steps. The coating step is to apply a release layer forming composition on the aforementioned surface layer A of the polyester film having the surface layer A, the aforementioned surface layer A is a layer substantially free of inorganic particles, and the release layer forming composition contains cationic hardening Type polydimethylsiloxane (a); the drying step is to heat and dry the aforementioned polyester film coated with the release layer forming composition, and the aforementioned heat drying has a first drying step and a subsequent second drying step, The drying temperature T1 in the aforementioned first drying step is higher than the drying temperature T2 in the aforementioned second drying step; and, the photocuring step is to irradiate active energy rays after the aforementioned drying step to harden the release layer forming composition.
若為本發明之製造方法,藉由增強第1乾燥條件(加強乾燥)防止構成離型層之樹脂的凝聚,可獲得具有高平滑性之離型層。 進而,藉由將離型層形成組成物中之溶媒的SP值設為預定值,可防止構成離型層之樹脂的凝聚,可獲得具有高平滑性之離型層。 如此般,本發明中第1乾燥步驟具有預定的條件,於一態樣中,藉由使用特定的溶劑,可獲得具有高平滑性之離型層。 According to the production method of the present invention, by enhancing the first drying condition (enhanced drying) to prevent aggregation of the resin constituting the release layer, a release layer with high smoothness can be obtained. Furthermore, by setting the SP value of the solvent in the release layer-forming composition to a predetermined value, aggregation of the resin constituting the release layer can be prevented, and a release layer having high smoothness can be obtained. In this way, the first drying step in the present invention has predetermined conditions, and in one aspect, a release layer with high smoothness can be obtained by using a specific solvent.
本發明之離型膜之製造方法依序具有:塗布步驟,係將至少含有陽離子硬化型聚二甲基矽氧烷(a)之離型層形成組成物塗布在聚酯膜之實質上不含無機粒子的表面層A上;乾燥步驟,係於塗布後將膜例如使用乾燥爐來進行加熱乾燥;以及,光硬化步驟,係於加熱乾燥後使用活性能量線來進行硬化。尤其,較佳為採用依序進行塗布步驟、乾燥步驟、光硬化步驟之方法。The manufacturing method of the release film of the present invention comprises in sequence: a coating step of coating a release layer-forming composition containing at least cation-curable polydimethylsiloxane (a) on the polyester film which does not substantially contain On the surface layer A of the inorganic particles; the drying step is to heat dry the film, for example, using a drying oven; and the photocuring step is to harden the film using active energy rays after heat drying. In particular, it is preferable to employ a method of sequentially performing a coating step, a drying step, and a photocuring step.
依據本發明之製造方法,發現藉由在塗布步驟的製造條件上下功夫,可實現具有高平滑性之離型層。具體而言,藉由於離型層形成組成物中含有SP值(δ)為14至17之有機溶媒,可抑制陽離子硬化型聚二甲基矽氧烷(a)之凝聚,可獲得優異之離型層。SP值(δ)可用於預測物質之溶解性,SP值(δ)為14至17之有機溶媒對於陽離子硬化型聚二甲基矽氧烷(a)展現優異之溶解性。因此,於塗布步驟後之乾燥步驟中,即便有機溶媒乾燥而提高了離型層形成組成物中之陽離子硬化型聚二甲基矽氧烷(a)的濃度,仍可保持在均勻溶解的狀態,不會發生凝聚而良好地均平,可獲得平滑的離型層。According to the production method of the present invention, it was found that a high-smooth release layer can be realized by concentrating on the production conditions of the coating step. Specifically, by containing an organic solvent with an SP value (δ) of 14 to 17 in the composition for forming the release layer, the aggregation of the cation-hardening polydimethylsiloxane (a) can be suppressed, and an excellent release layer can be obtained. type layer. The SP value (δ) can be used to predict the solubility of a substance, and organic solvents with an SP value (δ) of 14 to 17 exhibit excellent solubility for cationic hardening polydimethylsiloxane (a). Therefore, in the drying step after the coating step, even if the organic solvent is dried to increase the concentration of the cation-curable polydimethylsiloxane (a) in the release layer forming composition, it can still be maintained in a uniformly dissolved state. , without agglomeration and well-leveled, a smooth release layer can be obtained.
離型層形成組成物中所含SP值(δ)為14至17之有機溶媒之含量相對於離型層形成組成物100質量份,以10質量%以上為佳,以15質量%以上為更佳。若為10質量%以上,由於在乾燥中,陽離子硬化型聚二甲基矽氧烷(a)可保持在長時間溶解之狀態,故不用擔心乾燥中出現凝聚造成平滑性惡化故較佳。例如,SP值(δ)為14至17之有機溶媒之含量相對於離型層形成組成物100質量份為80質量%以下,例如可為65質量%以下、未達50質量%。The content of the organic solvent having an SP value (δ) of 14 to 17 contained in the release layer forming composition is preferably 10% by mass or more, more preferably 15% by mass or more, based on 100 parts by mass of the release layer forming composition good. If it is 10% by mass or more, the cation-curable polydimethylsiloxane (a) can be kept in a dissolved state for a long time during drying, so there is no fear of deterioration of smoothness due to aggregation during drying. For example, the content of the organic solvent having an SP value (δ) of 14 to 17 is 80% by mass or less, for example, 65% by mass or less and less than 50% by mass relative to 100 parts by mass of the release layer forming composition.
本說明書中之SP值(δ)係採用希德布朗溶解度參數。希德布朗溶解度參數在實驗上可從韓森溶解度參數(Hansen Solubility Parameters,HSP值)以式1的方式來算出。 SP值(δ)=((δ d) 2+(δ p) 2+(δ h) 2) 1/2・・・・・(式1) 此處(δ D)為分散力項,(δ P)為極性項,(δ H)為氫鍵力項,將希德布朗溶解度參數分解為3成分之思考方式為韓森溶解度參數。 此外,也可使用電腦軟體之HSPiP(Hansen Solubility Parameters in Practice)等來算出,本說明書所描述的值係使用在HSPiP ver4.0當中之資料庫所記載之HSP值,採用如同式1所算出之值。 The SP value (δ) in this specification is based on the Hidd Brown solubility parameter. The Hidden Brown solubility parameter can be experimentally calculated from the Hansen solubility parameters (Hansen Solubility Parameters, HSP value) in the manner of Equation 1. SP value (δ)=((δ d ) 2 +(δ p ) 2 +(δ h ) 2 ) 1/2・・・・・・(Formula 1) Here (δ D ) is the dispersion force term, (δ P ) is a polar term, (δ H ) is a hydrogen bond term, and the way of thinking of decomposing the Hidd Brown solubility parameter into three components is the Hansen solubility parameter. In addition, it can also be calculated using computer software HSPiP (Hansen Solubility Parameters in Practice), etc. The values described in this manual are the HSP values recorded in the database in HSPiP ver4. value.
SP值(δ)為14至17之有機溶媒可舉出例如正己烷(δ:14.9)、正庚烷(δ:15.3)、正辛烷(δ:15.5)、異丙醚(δ:15.8)、1,1-二乙氧基乙烷(δ:15.9)、甲基環己烷(δ:16.0)、環庚烷(δ:16.5)、環己烷(δ:16.8)等。Examples of organic solvents with an SP value (δ) of 14 to 17 include n-hexane (δ: 14.9), n-heptane (δ: 15.3), n-octane (δ: 15.5), isopropyl ether (δ: 15.8) , 1,1-diethoxyethane (δ: 15.9), methylcyclohexane (δ: 16.0), cycloheptane (δ: 16.5), cyclohexane (δ: 16.8), etc.
離型層形成組成物之塗布量以10g/m 2以下為佳,以8g/m 2以下為更佳。若塗布量為10g/m 2以下,例如以凹版塗敷方式進行塗布之際,位於膜與凹版輥間的接觸部變得不易發生紊液,可獲得平滑性優異之離型層故較佳。 The coating amount of the release layer forming composition is preferably not more than 10 g/m 2 , more preferably not more than 8 g/m 2 . If the coating amount is 10 g/ m2 or less, for example, when coating by gravure coating, the contact portion between the film and the gravure roll becomes less prone to turbulence, and a release layer with excellent smoothness can be obtained, so it is preferable.
本發明中,離型層形成物組成物所含溶媒以2種類以上為佳,以當中至少1種如前述般為SP值(δ)為14至17之溶媒、又至少1種為沸點為100℃以上為佳。藉由添加沸點為100℃以上之溶劑,可防止乾燥時之突沸,可使得塗膜均平,可提高乾燥後塗膜表面之平滑性。 溶媒添加量相對於離型層形成組成物全體以添加10質量%至70質量%左右為佳。沸點為100℃以上之溶劑例,可舉出甲苯、二甲苯、正辛烷、環己酮、甲基異丁酮、丙二醇單甲醚、丙二醇單丙醚、乙酸異丁酯、正丁醇等。 In the present invention, the solvent contained in the release layer forming composition is preferably two or more types, at least one of which is a solvent with an SP value (δ) of 14 to 17 as described above, and at least one of which has a boiling point of 100 °C or higher is preferred. By adding a solvent with a boiling point above 100°C, bumping during drying can be prevented, the coating film can be evened out, and the smoothness of the coating film surface after drying can be improved. The added amount of the solvent is preferably about 10% by mass to 70% by mass relative to the entire release layer forming composition. Examples of solvents with a boiling point above 100°C include toluene, xylene, n-octane, cyclohexanone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, isobutyl acetate, n-butanol, etc. .
本發明中,離型層形成組成物之塗液較佳為塗布前進行過濾。關於過濾方法並無特別限定可使用已知方法,以使用表面型(surface type)或深度型(depth type)、吸附型之匣式過濾器為佳。藉由使用匣式過濾器,由於可在將塗液從槽連續地送液至塗敷部時來使用,可高生產性、高效率地進行過濾故較佳。過濾器之過濾精度以使用可將1μm大小之物去除99%以上為佳,更佳為可將0.5μm大小之物過濾掉99%以上。藉由使用上述過濾精度的過濾器,可將形成離型層之塗液中所混入的異物予以去除,可減少附著於本發明之離型膜上的異物,可獲得平滑性優異之離型層故較佳。In the present invention, the coating solution of the release layer forming composition is preferably filtered before coating. There is no particular limitation on the filtering method, and a known method can be used, preferably a surface type, depth type, or adsorption type cassette filter. The use of a cassette filter is preferable because it can be used when continuously feeding the coating liquid from the tank to the coating part, and can perform filtration with high productivity and high efficiency. The filtration accuracy of the filter is preferably used to remove more than 99% of objects with a size of 1 μm, and more preferably to filter out more than 99% of objects with a size of 0.5 μm. By using the filter with the above-mentioned filtration precision, foreign matter mixed in the coating solution forming the release layer can be removed, foreign matter adhering to the release film of the present invention can be reduced, and a release layer with excellent smoothness can be obtained. So better.
上述塗液之塗布法可適用眾知的任意塗布法,例如可利用凹版塗布法或反向塗布法等輥式塗布法、線棒等之棒塗布法、模具塗布法、噴霧塗布法、氣刀塗布法等以往已知之方法。The coating method of the above-mentioned coating liquid can be applied to any known coating method, for example, a roll coating method such as a gravure coating method or a reverse coating method, a bar coating method such as a wire bar, a die coating method, a spray coating method, an air knife coating method, etc., can be used. A conventionally known method such as a coating method.
作為將離型層形成組成物塗布於基材膜上並進行乾燥之方法,可舉出眾知之熱風乾燥、紅外線加熱器等,以乾燥速度快的熱風乾燥為佳。以在乾燥爐內進行乾燥為佳,無特別限定可使用已知的乾燥爐。關於乾燥爐的方式,可為滾筒支撐(roll support)方式亦可為懸浮(floating)方式皆無妨,若以滾筒支撐方式,可調整乾燥時風量之範圍較廣,而可調配離型層之種類來調整風量等故較佳。As a method of coating and drying the release layer-forming composition on the base film, well-known hot air drying, infrared heater, etc. are mentioned, and hot air drying with a fast drying speed is preferable. Drying is preferably carried out in a drying oven, and known drying ovens can be used without particular limitation. As for the method of drying oven, it can be either roll support or floating. If the roller support is used, the air volume can be adjusted in a wide range during drying, and the type of release layer can be adjusted. It is better to adjust the air volume, etc.
乾燥步驟可分為乾燥初期之恆率乾燥步驟(以下稱為第1乾燥步驟)以及減率乾燥步驟(以下稱為第2乾燥步驟)這2個乾燥步驟。2個步驟以第1乾燥步驟、第2乾燥步驟之順序來連續為佳,可藉由在乾燥爐內劃分區域來區隔,第1(初期)乾燥步驟可使用第1乾燥爐來進行乾燥,第2(後期)乾燥步驟可使用第2乾燥爐來進行乾燥。The drying step can be divided into two drying steps: a constant rate drying step (hereinafter referred to as the first drying step) and a decreasing rate drying step (hereinafter referred to as the second drying step) in the initial stage of drying. The two steps are preferably continuous in the order of the first drying step and the second drying step, which can be separated by dividing the area in the drying furnace. The first (initial) drying step can be dried using the first drying furnace. In the second (later) drying step, drying can be performed using a second drying oven.
本發明人等發現為了提高離型層之平滑性,使得第1乾燥步驟中之乾燥溫度T1高於前述第2乾燥步驟中之乾燥溫度T2為重要。第1乾燥爐溫度與第2乾燥爐溫度以控制在後述範圍為佳。藉由此種條件進行製造,可縮短第1乾燥步驟中之恒率乾燥時間、拉長第2乾燥步驟中之減率乾燥時間,可獲得平面性優異之離型層故較佳。The present inventors found that in order to improve the smoothness of the release layer, it is important to make the drying temperature T1 in the first drying step higher than the drying temperature T2 in the second drying step. The temperature of the first drying furnace and the temperature of the second drying furnace are preferably controlled within the range described later. Manufacturing under such conditions can shorten the constant-rate drying time in the first drying step and lengthen the decreasing-rate drying time in the second drying step, so that a release layer with excellent planarity can be obtained, so it is preferable.
再者,本發明人等發現到提高第1乾燥爐內溫度來縮短恒率乾燥時間為重要。 更具體而言,乾燥溫度T1以90℃以上至180℃以下為佳,以100℃以上至150℃以下為佳。藉由提高第1乾燥爐內之溫度來縮短恒率乾燥時間,可防止離型層形成組成物中所含陽離子硬化型聚二甲基矽氧烷(a)之凝聚故較佳。第1乾燥爐之溫度愈高,則恒率乾燥時間愈短故較佳,但若溫度過高則會因為熱造成膜之平面性惡化,故以180℃以下為佳。若為90℃以上,則乾燥能力成為充分故較佳。 Furthermore, the present inventors have found that it is important to increase the temperature in the first drying furnace to shorten the constant rate drying time. More specifically, the drying temperature T1 is preferably above 90°C and below 180°C, preferably above 100°C and below 150°C. It is preferable to shorten the constant rate drying time by increasing the temperature in the first drying oven to prevent aggregation of the cation-curable polydimethylsiloxane (a) contained in the release layer forming composition. The higher the temperature of the first drying oven, the shorter the constant-rate drying time is, so it is better, but if the temperature is too high, the flatness of the film will be deteriorated due to heat, so it is better to be below 180°C. If it is 90 degreeC or more, since drying ability becomes sufficient, it is preferable.
第2乾燥爐內溫度以60℃以上至140℃以下為佳,以80℃以上至120℃以下為更佳。第2乾燥步驟中,藉由延長乾燥時間則可在不致使得光硬化前的離型層表面成為粗糙的前提下進行乾燥,可提高離型層之平滑性故較佳。The temperature in the second drying furnace is preferably above 60°C and below 140°C, more preferably above 80°C and below 120°C. In the second drying step, it is preferable to increase the smoothness of the release layer by prolonging the drying time without roughening the surface of the release layer before photohardening.
例如,第1乾燥步驟中之恒率乾燥時間以少於第2乾燥步驟中之減率乾燥時間為佳。藉此,可防止膜之平面性惡化,進而,可在不致使得光硬化前的離型層表面成為粗糙的前提下進行乾燥,可提高離型層之平滑性。For example, the constant-rate drying time in the first drying step is preferably shorter than the decreasing-rate drying time in the second drying step. Thereby, deterioration of planarity of the film can be prevented, furthermore, drying can be performed without roughening the surface of the release layer before photohardening, and the smoothness of the release layer can be improved.
塗布後直到進入第1乾燥爐內之時間以0.1秒以上至2.5秒以內為佳,以0.1秒以上至2.0秒以內為佳,愈短愈佳。藉由縮短進入第1乾燥爐內所需時間,可縮短第1乾燥步驟中之乾燥時間,可抑制陽離子硬化型聚二甲基矽氧烷(a)之凝聚,獲得平滑性優異之離型層故較佳。進入乾燥爐內為止所需時間可從加工速度與加工機台之結構來算出。The time after coating until entering the first drying oven is preferably from 0.1 second to 2.5 seconds, preferably from 0.1 second to 2.0 seconds, and the shorter the better. By shortening the time required to enter the first drying oven, the drying time in the first drying step can be shortened, the aggregation of cationic hardening polydimethylsiloxane (a) can be suppressed, and a release layer with excellent smoothness can be obtained So better. The time required to enter the drying furnace can be calculated from the processing speed and the structure of the processing machine.
本發明之製造方法包含於乾燥步驟後照射活性能量線來使得離型層形成組成物產生硬化之光硬化步驟。 於光硬化步驟中,藉由照射活性能量線來進行乾燥後離型層形成組成物之陽離子硬化反應。所使用的活性能量線可使用紫外線、電子束等已知的技術,以使用紫外線為佳。使用紫外線時的累計光量能以照度與照射時間之乘積來表示。例如,以10mJ/cm 2至500mJ/cm 2為佳。藉由設定為前述下限以上,可使得離型層充分硬化故較佳。藉由設為前述上限以下,可抑制照射時之熱造成膜受到熱損傷,可維持離型層表面之平滑性故較佳。 The production method of the present invention includes a photocuring step of hardening the release layer forming composition by irradiating active energy rays after the drying step. In the photohardening step, the cationic hardening reaction of the dried release layer forming composition proceeds by irradiating active energy rays. The active energy ray to be used can use known techniques such as ultraviolet rays and electron beams, and it is preferable to use ultraviolet rays. The cumulative amount of light when using ultraviolet rays can be expressed as the product of illuminance and irradiation time. For example, it is preferably 10mJ/cm 2 to 500mJ/cm 2 . By setting it as more than the said minimum, since a release layer can fully harden, it is preferable. By setting it below the said upper limit, thermal damage to a film by the heat at the time of irradiation can be suppressed, and the smoothness of the release layer surface can be maintained, and it is preferable.
照射活性能量線時,將膜內面以背托(backup)輥來保持為佳。藉由設置背托輥,可將相對於活性能量線源之距離保持在一定而能均勻地照射故較佳。此外,以一邊冷卻背托輥表面來冷卻膜一邊照射活性能量線為佳。藉由進行冷卻,即便照射活性能量線之情況,膜也不易因受熱而受到損傷,可維持離型層表面之平滑性故較佳。When irradiating active energy rays, it is preferable to hold the inner surface of the film with a backup roll. By providing a back roller, it is preferable to maintain a constant distance from the active energy ray source and to uniformly irradiate. In addition, it is preferable to irradiate the active energy ray while cooling the surface of the back roller to cool the film. By cooling, even when active energy rays are irradiated, the film is less likely to be damaged by heat, and the smoothness of the surface of the release layer can be maintained, so it is preferable.
於一態樣中,本發明之製造方法提供一種離型膜之製造方法,用以製造含無機化合物之樹脂片。In one aspect, the manufacturing method of the present invention provides a manufacturing method of a release film for manufacturing a resin sheet containing an inorganic compound.
(樹脂片) 本發明中之樹脂片只要是含樹脂之片則並無特別限定。於一態樣中,本發明之離型膜為用以成型出含無機化合物之樹脂片的離型膜。作為無機化合物可舉例出金屬粒子、金屬氧化物、礦物等,例如可舉例出碳酸鈣、二氧化矽粒子、氧化鋁粒子、鈦酸鋇粒子等。本發明由於具有平滑性高的離型層,故即便是樹脂片含有此等無機化合物之態樣,也可抑制可能是起因於無機化合物之缺點(例如樹脂片之破損、樹脂片變得難以自離型層剝離之問題)。 形成樹脂片之樹脂成分可依據用途來適宜選擇。於一態樣中,含無機化合物之樹脂片為陶瓷生坯。例如,陶瓷生坯可含有鈦酸鋇作為無機化合物。此外,樹脂成分例如可含有聚乙烯醇縮丁醛系樹脂。 於一態樣中,樹脂片之厚度為0.2μm以上至1.0μm以下。 例如,本發明可提供一種離型膜之製造方法,此離型膜係用以製造含此等無機化合物之樹脂片。此外,本發明中之樹脂片成型用離型膜之製造方法也可包含:成型出厚度為0.2μm以上至1.0μm以下之樹脂片的步驟。 (resin sheet) The resin sheet in the present invention is not particularly limited as long as it is a resin-containing sheet. In one aspect, the release film of the present invention is a release film for forming a resin sheet containing an inorganic compound. Examples of the inorganic compound include metal particles, metal oxides, minerals, and the like, for example, calcium carbonate, silica particles, alumina particles, barium titanate particles, and the like. Since the present invention has a high-smooth release layer, even if the resin sheet contains such inorganic compounds, it can suppress the defects that may be caused by the inorganic compounds (such as damage to the resin sheet, and the resin sheet becomes difficult to self-destruct). The problem of peeling of the release layer). The resin component forming the resin sheet can be appropriately selected according to the application. In one aspect, the resin sheet containing the inorganic compound is a ceramic green body. For example, a ceramic green body may contain barium titanate as an inorganic compound. In addition, the resin component may contain polyvinyl butyral resin, for example. In one aspect, the thickness of the resin sheet is not less than 0.2 μm and not more than 1.0 μm. For example, the present invention can provide a method for producing a release film for producing a resin sheet containing these inorganic compounds. In addition, the method for manufacturing a release film for forming a resin sheet in the present invention may also include: a step of forming a resin sheet with a thickness of not less than 0.2 μm and not more than 1.0 μm.
(陶瓷生坯與陶瓷電容器) 一般而言,積層陶瓷電容器具有長方體狀之陶瓷素體。於陶瓷素體之內部係使得第1內部電極與第2內部電極沿著厚度方向交互地設置。第1內部電極係露出於陶瓷素體之第1端面。於第1端面上設有第1外部電極。第1內部電極於第1端面和第1外部電極呈電性連接。第2內部電極係露出於陶瓷素體之第2端面。於第2端面上設有第2外部電極。第2內部電極於第2端面和第2外部電極呈電性連接。 (Ceramic green body and ceramic capacitor) In general, a multilayer ceramic capacitor has a rectangular parallelepiped ceramic body. Inside the ceramic body, the first internal electrodes and the second internal electrodes are arranged alternately along the thickness direction. The first internal electrode is exposed on the first end face of the ceramic body. A first external electrode is provided on the first end face. The first internal electrode is electrically connected to the first external electrode on the first end surface. The second internal electrode is exposed on the second end surface of the ceramic body. A second external electrode is provided on the second end surface. The second internal electrode is electrically connected to the second external electrode on the second end surface.
於一態樣中,本發明之離型膜為陶瓷生坯製造用離型膜,為了製造此種積層陶瓷電容器而使用。 例如,使用本發明之陶瓷生坯製造用離型膜來成型出陶瓷生坯之陶瓷生坯之製造方法,可成型出具有0.2μm以上至1.0μm以下之厚度的陶瓷生坯。 更詳細而言,例如採以下方式來製造陶瓷生坯。首先,將本發明之離型膜當作載體膜使用,塗布上用以構成陶瓷素體的陶瓷漿料並進行乾燥。陶瓷生坯之厚度逐漸要求為0.2μm至1.0μm之極薄品。於經過塗布、乾燥之陶瓷生坯上,印刷用以構成第1內部電極或是第2內部電極之導電層。可藉由將陶瓷生坯、印刷了用以構成第1內部電極之導電層的陶瓷生坯以及印刷了用以構成第2內部電極之導電層的陶瓷生坯加以適宜積層並加壓,獲得母積層體。將母積層體分切為複數個,製作生陶瓷素體。藉由對生陶瓷素體進行燒成來獲得陶瓷素體。之後,可藉由形成第1外部電極以及第2外部電極來完成積層陶瓷電容器。 [實施例] In one aspect, the release film of the present invention is a release film for manufacturing a ceramic green body, and is used to manufacture such a multilayer ceramic capacitor. For example, the method of manufacturing a ceramic green body that uses the release film for manufacturing a ceramic green body of the present invention to mold a ceramic green body can mold a ceramic green body having a thickness of not less than 0.2 μm and not more than 1.0 μm. More specifically, ceramic green bodies are produced, for example, as follows. First, the release film of the present invention is used as a carrier film, and the ceramic slurry for constituting the ceramic body is coated and dried. The thickness of the ceramic green body is gradually required to be extremely thin from 0.2 μm to 1.0 μm. On the coated and dried ceramic green body, the conductive layer for constituting the first internal electrode or the second internal electrode is printed. The matrix can be obtained by appropriately laminating and pressing ceramic green bodies, ceramic green bodies printed with a conductive layer constituting a first internal electrode, and ceramic green bodies printed with a conductive layer constituting a second internal electrode. laminated body. The mother laminated body is divided into plural pieces to produce a green ceramic element body. The ceramic body is obtained by firing the raw ceramic body. Thereafter, a multilayer ceramic capacitor can be completed by forming the first external electrode and the second external electrode. [Example]
以下,以實施例對本發明進而詳細說明,但本發明完全不受限於這些實施例。本發明所使用之特性值係使用下述方法進行評價。Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples at all. The characteristic values used in the present invention were evaluated using the following methods.
(離型層厚度) 對切出的離型膜進行樹脂包埋,使用超級切片機進行超薄切片化。之後,使用日本電子製JEM2100穿透電子顯微鏡進行截面觀察,自所觀察到的TEM圖像測定離型層之膜厚。當厚度過薄以截面觀察無法正確地進行評價之情況,改用反射分光膜厚計(大塚電子公司製,FE-3000)來進行測定。 (release layer thickness) Resin-embed the cut release film, and perform ultra-thin sectioning with a super microtome. Thereafter, cross-sectional observation was performed using a JEM2100 transmission electron microscope manufactured by JEOL Ltd, and the film thickness of the release layer was measured from the observed TEM image. When the thickness is too thin to be evaluated correctly by cross-sectional observation, it is measured using a reflection spectroscopic film thickness meter (manufactured by Otsuka Electronics Co., Ltd., FE-3000) instead.
(離型層重量) 本說明書中,採用離型層每厚度1μm之重量作為1g/m 2所算出之重量值。例如,當以前述方法所測定之離型層厚度為0.2μm之情況,離型層之總重量為0.2g/m 2。此外,離型層中所含陽離子硬化型聚二甲基矽氧烷(a)之重量、陽離子硬化型樹脂(b)之重量、酸產生劑(c)之重量係採用從離型層形成組成物中所含各成分之調配比率與離型層之總重量所計算出的值。例如,當離型層厚度為0.2μm、陽離子硬化型聚二甲基矽氧烷(a)之離型層重量比率為5質量份之情況,離型層中所含陽離子硬化型聚二甲基矽氧烷(a)之重量為0.01g/m 2。此外,離型層重量比率(質量%)係以成分(a)與成分(b)之合計為100質量份來計算。 (Release layer weight) In this specification, the weight of the release layer per thickness of 1 μm is used as the weight value calculated by 1 g/m 2 . For example, when the thickness of the release layer measured by the aforementioned method is 0.2 μm, the total weight of the release layer is 0.2 g/m 2 . In addition, the weight of the cation-curable polydimethylsiloxane (a), the weight of the cation-curable resin (b), and the weight of the acid generator (c) contained in the release layer are based on the composition formed from the release layer. The value calculated from the blending ratio of each component contained in the product and the total weight of the release layer. For example, when the thickness of the release layer is 0.2 μm and the weight ratio of the release layer of cation-curing polydimethylsiloxane (a) is 5 parts by mass, the cation-curing polydimethylsiloxane contained in the release layer The weight of siloxane (a) is 0.01 g/m 2 . In addition, the release layer weight ratio (mass %) is calculated with the total of the component (a) and the component (b) being 100 mass parts.
(離型層形成組成物之塗布量) 採用從塗布步驟所使用之離型層形成組成物之液消耗重量與加工面積所算出之值。 (Coating amount of release layer forming composition) The value calculated from the liquid consumption weight and the processing area of the release layer forming composition used in the coating process was used.
(自塗布後至第1乾燥爐為止的時間) 採用從塗布部至第1乾燥爐為止的膜行進距離與加工速度所算出之值。 (Time from coating to 1st drying oven) The value calculated from the film travel distance and processing speed from the coating section to the first drying furnace was used.
(區域表面粗度Sa、最大突起高度Sp) 使用非接觸表面形狀量測系統(VertScanR550H-M100),以下述條件進行測定。區域表面平均粗度(Sa)係採用5次測定之平均值,最大突起高度(Sp)係進行7次測定而採用摒除了最大值與最小值後的5次測定結果中之最大值。 (測定條件) ・測定模式:WAVE模式 ・物鏡:50倍 ・0.5×Tube透鏡 ・測定面積187μm×139μm (分析條件) ・面校正:4次校正 ・內插處理:完全內插 (area surface roughness Sa, maximum protrusion height Sp) The measurement was performed under the following conditions using a non-contact surface shape measurement system (VertScan R550H-M100). The area surface average roughness (Sa) is the average value of 5 measurements, and the maximum protrusion height (Sp) is the maximum value of the 5 measurement results after excluding the maximum and minimum values from 7 measurements. (measurement conditions) ・Measurement mode: WAVE mode ・Objective lens: 50 times ・0.5×Tube lens ・Measurement area 187μm×139μm (analysis conditions) ・Surface correction: 4 corrections ・Interpolation processing: full interpolation
(高度10nm以上之突起數、高度5nm以上之突起數) 使用測定了上述最大突起高度之共7次的測定值當中顯示中心值之測定數據,進行了粒子分析。粒子分析係使用VertscanR550H-M100之分析軟體以下述條件來求出。以上述區域表面粗度、最大突起高度測定以及同面積之測定面積來進行粒子分析,算出最高度為10nm以上之突起數、或是5nm以上之突起數。突起數採用以1mm 2換算來轉換後的值。 (粒子分析條件) ・面校正:4次校正 ・保管處理:完全內插 ・突分析 ・基準高度:零面 (The number of protrusions with a height of 10 nm or more, the number of protrusions with a height of 5 nm or more) Particle analysis was performed using measurement data showing a central value among the measured values of the above-mentioned maximum protrusion height measured 7 times in total. Particle analysis was obtained under the following conditions using Vertscan R550H-M100 analysis software. Particle analysis is carried out by measuring the surface roughness of the above region, the maximum protrusion height, and the measured area of the same area, and calculating the number of protrusions with a maximum height of 10 nm or more, or the number of protrusions with a maximum height of 5 nm or more. As for the number of protrusions, the values converted in 1 mm 2 conversion were used. (Particle analysis conditions) ・Surface calibration: 4 times calibration ・Storage processing: full interpolation ・Protrusion analysis ・Reference height: zero plane
(陶瓷片剝離力) 將由下述材料所構成之漿料組成物I以10分鐘攪拌混合,使用珠磨機以直徑0.5mm之氧化鋯珠進行10分鐘分散,獲得1次分散體。之後將由下述材料所構成之漿料組成物II以成為(漿料組成物I):(漿料組成物II)=3.4:1.0之比率加入至1次分散體,使用珠磨機以直徑0.5mm之氧化鋯珠進行10分鐘的2次分散,獲得陶瓷漿料。 (漿料組成物I) 甲苯 22.3質量份 乙醇 18.3質量份 鈦酸鋇(平均粒徑100nm) 57.5質量份 賀磨捷諾魯L-18(花王公司製) 1.9質量份 (漿料組成物II) 甲苯 39.6質量份 乙醇 39.6質量份 鄰苯二甲酸二辛酯 3.3質量份 聚乙烯醇縮丁醛(積水化學公司製艾斯列克BM-S) 16.3質量份 1-乙基-3-甲基咪唑鎓乙基硫酸鹽 0.5質量份 其次,對於所得之離型膜樣品之離型面使用施用機(applicator)以乾燥後之漿料成為1.0μm的方式進行塗敷,以60℃乾燥1分鐘,獲得具陶瓷生坯之離型膜。將所得之具陶瓷生坯之離型膜利用去電機(Keyence公司製,SJ-F020)去電後,使用剝離試験機(協和界面科學公司製,VPA-3,荷重元荷重0.1N),以剝離角度90度、剝離溫度25℃、剝離速度10m/min進行剝離。關於剝離方向,係於剝離試驗機附屬之SUS(不鏽鋼)板上貼附雙面接著膠帶(日東電工公司製,No.535A),於雙面接著膠帶上以陶瓷生坯側來和雙面膠帶進行接著的形式將離型膜加以固定,以拉扯離型膜側的形式進行剝離。算出所得測定值當中之剝離距離為20mm至70mm之剝離力的平均值,將該值作為剝離力。測定實施共5次,採用剝離力之平均值來進行評價。從所得剝離力之數值以下述基準來判定。 〇:0.1mN/mm以上至未達1.0mN/mm ×:1.0mN/mm以上 (Peel force of ceramic sheet) The slurry composition I composed of the following materials was stirred and mixed for 10 minutes, and dispersed with zirconia beads with a diameter of 0.5 mm using a bead mill for 10 minutes to obtain a primary dispersion. Afterwards, the slurry composition II composed of the following materials was added to the primary dispersion at a ratio of (slurry composition I): (slurry composition II) = 3.4: 1.0, using a bead mill with a diameter of 0.5 mm zirconia beads were dispersed twice for 10 minutes to obtain a ceramic slurry. (slurry composition I) Toluene 22.3 parts by mass Ethanol 18.3 parts by mass Barium titanate (average particle size 100nm) 57.5 parts by mass Hemojie Nuolu L-18 (manufactured by Kao Corporation) 1.9 parts by mass (Slurry Composition II) Toluene 39.6 parts by mass Ethanol 39.6 parts by mass Dioctyl phthalate 3.3 parts by mass Polyvinyl butyral (ESLEC BM-S manufactured by Sekisui Chemical Co., Ltd.) 16.3 parts by mass 1-Ethyl-3-methylimidazolium ethyl sulfate 0.5 parts by mass Next, apply an applicator to the release surface of the obtained release film sample so that the dried slurry becomes 1.0 μm, and dry at 60°C for 1 minute to obtain a release film with a ceramic green body . After de-energizing the obtained release film with a ceramic green body with a de-energizer (manufactured by Keyence, SJ-F020), use a peeling tester (manufactured by Kyowa Interface Science Co., Ltd., VPA-3, load cell load 0.1N) to Peeling was performed at a peeling angle of 90 degrees, a peeling temperature of 25° C., and a peeling speed of 10 m/min. Regarding the peeling direction, stick double-sided adhesive tape (manufactured by Nitto Denko Co., Ltd., No. 535A) on the SUS (stainless steel) plate attached to the peeling tester, and place the double-sided adhesive tape on the ceramic green side on the double-sided adhesive tape In the following form, the release film is fixed, and the release film side is pulled to peel off. The average value of the peeling force at which the peeling distance was 20 mm to 70 mm among the obtained measured values was calculated, and this value was made into peeling force. The measurement was carried out 5 times in total, and the average value of the peeling force was used for evaluation. From the obtained value of peeling force, it judged by the following reference|standard. 〇: 0.1mN/mm or more to less than 1.0mN/mm ×: 1.0mN/mm or more
(陶瓷生坯之針孔評價) 和前述陶瓷漿料之剝離性評價同樣地,於離型膜之離型面成型出厚度1μm之陶瓷生坯。其次,從成型出之具陶瓷生坯之離型膜來剝離離型膜,獲得陶瓷生坯。在所得陶瓷生坯之膜寬度方向之中央區域,以25cm 2之範圍自陶瓷漿料塗布面的相反面照光,觀察光穿透所能見到的針孔產生狀況,以下述基準進行目視判定。 〇:無產生針孔 ×:產生針孔達1個以上 (Evaluation of pinholes in ceramic green body) Similar to the evaluation of peelability of the above-mentioned ceramic slurry, a ceramic green body with a thickness of 1 μm was molded on the release surface of the release film. Secondly, the release film is peeled off from the molded release film with the ceramic green body to obtain the ceramic green body. In the central region of the obtained ceramic green body in the film width direction, light was irradiated from the opposite side of the ceramic slurry coating surface in a range of 25 cm 2 , and the occurrence of pinholes visible through light penetration was observed, and visual judgment was performed based on the following criteria. 〇: No pinholes occurred ×: One or more pinholes occurred
(聚對苯二甲酸乙二酯顆粒(PET (I))之製備) 在酯化反應裝置方面使用由具有攪拌裝置、分餾器、原料裝填口以及生成物取出口之3段的完全混合槽所構成之連續酯化反應裝置。將TPA(對苯二甲酸)設定為2噸/小時,將EG(乙二醇)相對於TPA 1莫耳設為2莫耳,將三氧化銻相對於生成PET使得Sb原子成為160ppm的量,將這些漿料連續供給於酯化反應裝置之第1酯化反應罐,在常壓下以平均滯留時間4小時、255℃進行反應。其次,將第1酯化反應罐內之反應生成物連續地取出至系統外而供給至第2酯化反應罐,於第2酯化反應罐內將自第1酯化反應罐所餾除的EG相對於生成PET供給8質量%,進而,添加含有Mg原子相對於生成PET成為65ppm的量的乙酸鎂四水合鹽之EG溶液、以及含有P原子相對於生成PET成為40ppm之量的TMPA(磷酸三甲酯)之EG溶液,在常壓下以平均滯留時間1小時、260℃進行反應。其次,將第2酯化反應罐之反應生成物連續地取出至系統外而供給至第3酯化反應罐,一邊將使用高壓分散機(日本精機公司製)以39MPa(400kg/cm 2)之壓力進行了平均處理次數5路徑的分散處理後之平均粒徑0.9μm之多孔質矽膠0.2質量%、以及聚丙烯酸之銨鹽相對於每單位碳酸鈣附著了1質量%之平均粒徑為0.6μm之合成碳酸鈣0.4質量%分別當作10%之EG漿料來添加,一邊在常壓下以平均滯留時間0.5小時、260℃進行反應。將在第3酯化反應罐內所生成之酯化反應生成物連續地供給至3段之連續縮聚反應裝置來進行縮聚,以95%切面直徑為20μm之不鏽鋼繊維經燒結之過濾器來進行過濾後,進行超過濾而擠出至水中,冷卻後切割為碎片狀,獲得固有黏度0.60dl/g之PET碎片(以下稱為PET(I))。PET碎片中之滑劑含量為0.6質量%。 (Preparation of Polyethylene Terephthalate Granules (PET (I))) As an esterification reaction device, a three-stage complete mixing tank with a stirring device, a fractionator, a raw material charging port, and a product outlet is used. A continuous esterification reaction device. TPA (terephthalic acid) was set to 2 tons/hour, EG (ethylene glycol) was set to 2 moles per 1 mole of TPA, and antimony trioxide was set in such an amount that Sb atoms became 160 ppm with respect to the formed PET, These slurries were continuously supplied to the 1st esterification reaction tank of the esterification reaction apparatus, and it reacted at 255 degreeC with an average residence time of 4 hours under normal pressure. Next, the reaction product in the first esterification reaction tank is continuously taken out of the system and supplied to the second esterification reaction tank, and in the second esterification reaction tank, the EG was supplied in an amount of 8% by mass relative to the resulting PET, and further, an EG solution containing magnesium acetate tetrahydrate in an amount of 65 ppm of Mg atoms relative to the resulting PET, and TMPA (phosphoric acid) containing 40 ppm of P atoms relative to the resulting PET were added. The EG solution of trimethyl ester) was reacted at 260°C with an average residence time of 1 hour under normal pressure. Next, the reaction product of the second esterification reaction tank was continuously taken out of the system and supplied to the third esterification reaction tank, while using a high-pressure disperser (manufactured by Nippon Seiki Co., Ltd.) at 39MPa (400kg/cm 2 ) 0.2% by mass of porous silica gel with an average particle size of 0.9 μm after pressure-treated average number of times of dispersion treatment of 5 paths, and an average particle size of 0.6 μm with 1 mass % of ammonium polyacrylic acid attached per unit of calcium carbonate 0.4% by mass of synthetic calcium carbonate was added as 10% EG slurry, and the reaction was carried out at 260° C. with an average residence time of 0.5 hours under normal pressure. The esterification reaction product generated in the third esterification reaction tank is continuously supplied to the three-stage continuous polycondensation reaction device for polycondensation, and 95% of the sintered stainless steel fiber with a cross-sectional diameter of 20 μm is used for filtration. Afterwards, carry out ultrafiltration and extrude into water, cut into fragments after cooling, obtain the PET fragment (hereinafter referred to as PET (I)) of inherent viscosity 0.60dl/g. The content of the slip agent in the PET chips was 0.6% by mass.
(聚對苯二甲酸乙二酯顆粒(PET(II))之製備) 另一方面,於上述PET(I)碎片之製造中,獲得了完全不含碳酸鈣、二氧化矽等粒子之固有黏度0.62dl/g之PET碎片(以下稱為PET(II))。 (Preparation of Polyethylene Terephthalate Granules (PET(II))) On the other hand, in the production of the above-mentioned PET (I) chips, PET chips with an intrinsic viscosity of 0.62 dl/g (hereinafter referred to as PET (II)) completely free of particles such as calcium carbonate and silicon dioxide were obtained.
(積層膜X1之製造) 將這些PET碎片乾燥後,以285℃熔融,藉由個別的擠出機以290℃熔融,利用95%切面直徑為15μm之不鏽鋼繊維經燒結之過濾器以及95%切面直徑為15μm之不鏽鋼粒子經燒結之過濾器來進行2段過濾,於進料塊內匯集,以PET(I)成為表面層B(相反於離型面側層)、PET(II)成為表面層A(離型面側層)的方式來積層,以45m/分鐘的速度擠出(澆鑄)成為片狀,利用静電密接法在30℃之澆鑄轉筒上進行静電密接、冷卻,獲得固有黏度為0.59dl/g之未延伸聚對苯二甲酸乙二酯片。層比率以各擠出機之吐出量計算成為PET(I)/(II)=60質量%/40質量%的方式進行了調整。其次,將此未延伸片以紅外線加熱器進行加熱後,以輥溫度80℃藉由輥間的速度差在縱向上進行3.5倍延伸。之後,引導至拉幅機,以140℃在橫向進行4.2倍之延伸。其次,於熱固定區以210℃進行熱處理。之後,於橫向以170℃進行2.3%之緩和處理,獲得厚度31μm之雙軸延伸聚對苯二甲酸乙二酯膜X1。所得膜X1之表面層A之Sa為1nm,表面層B之Sa為28nm。 (Manufacture of laminated film X1) After drying these PET flakes, they were melted at 285°C, melted at 290°C by a separate extruder, and sintered filters with 95% stainless steel fibers with a cross-sectional diameter of 15 μm and 95% stainless steel particles with a cross-sectional diameter of 15 μm were passed through The sintered filter is used for 2-stage filtration, which is collected in the feed block, and PET (I) becomes the surface layer B (opposite to the side layer of the release surface), and PET (II) becomes the surface layer A (side layer of the release surface) ) to laminate, extrude (cast) at a speed of 45m/min to form a sheet, use the electrostatic bonding method to carry out static bonding and cooling on a casting drum at 30°C, and obtain an intrinsic viscosity of 0.59dl/g Unstretched polyethylene terephthalate sheet. The layer ratio was adjusted so that PET(I)/(II)=60% by mass/40% by mass was calculated based on the discharge amount of each extruder. Next, after heating this unstretched sheet with an infrared heater, it stretched 3.5 times in the longitudinal direction at a roll temperature of 80° C. with a speed difference between the rolls. Thereafter, it was guided to a tenter and stretched 4.2 times in the lateral direction at 140°C. Next, heat treatment is performed at 210° C. in a heat-fixing zone. Thereafter, a relaxation treatment of 2.3% was performed at 170° C. in the lateral direction to obtain a biaxially stretched polyethylene terephthalate film X1 with a thickness of 31 μm. The Sa of the surface layer A of the obtained film X1 was 1 nm, and the Sa of the surface layer B was 28 nm.
(積層膜X2之製造) 積層膜X2係使用厚度25μm之E5101(東洋紡酯(註冊商標)膜,東洋紡公司製)。E5101為在表面層A以及表面層B含有粒子之構成。積層膜X2之表面層A之Sa為24nm,表面層B之Sa為24nm。 (Manufacture of laminated film X2) For the laminated film X2, E5101 (Toyobo Ester (registered trademark) film, manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm was used. E5101 is a composition that contains particles in surface layer A and surface layer B. The Sa of the surface layer A of the multilayer film X2 is 24 nm, and the Sa of the surface layer B is 24 nm.
(陽離子硬化型聚二甲基矽氧烷(a)) (a)-1:UVPOLY215(荒川化學工業製,固形物100%) (cationically hardening polydimethylsiloxane (a)) (a)-1: UVPOLY215 (manufactured by Arakawa Chemical Industries, solid content 100%)
(陽離子硬化型樹脂(b)) (b)-1:Celloxide 2021P(Daicel公司製,固形物100%) (b)-2:X-40-2670(信越化學工業製,固形物100%) (cationically curable resin (b)) (b)-1: Celloxide 2021P (manufactured by Daicel, solid content 100%) (b)-2: X-40-2670 (manufactured by Shin-Etsu Chemical Co., Ltd., solid content 100%)
(酸產生劑(c)) (c)-1:CPI-101A(San-Apro公司製,固形物50%) (acid generator (c)) (c)-1: CPI-101A (manufactured by San-Apro, 50% solids)
(實施例1) 將下述組成之離型層形成組成物1通過可將0.5μm以上之異物99%以上去除的過濾器之後,使用反向凹版以塗布量成為5.0g/m 2的方式塗敷於積層膜X1之表面層A上。之後,以經過0.5秒後進入第1乾燥爐的方式調整加工速度,以第1乾燥爐溫度120℃、第2乾燥爐溫度90℃來連續地進行加熱乾燥。乾燥步驟後,於冷卻輥上以紫外線照射機(Heraeus公司製,H bulb)照射累計光量100mJ/cm 2之紫外線,使得離型層硬化以獲得樹脂片成型用離型膜。此外,進行所得離型膜之平滑性、剝離性、以及針孔評價的結果,如表1所示獲得了良好的結果。 如此般,所得樹脂片成型用離型膜為可製造例如厚度為0.2μm以上至1.0μm以下之樹脂片的離型膜。 此外,表中所記載之各成分(a)、(b)、(c)之重量(mg/m 2)表示每單位固形物之含有比率(各成分之重量相對於離型層總重量)。 (離型層形成組成物1) 甲基乙基酮 24.000質量份 (SP值(δ):19.1,(δ D):16.0,(δ P):9.0,(δ H):5.1) 甲苯 24.000質量份 (SP值(δ):18.2,(δ D):18.0,(δ P):1.4,(δ H):2.0) 正庚烷 48.000質量份 (SP值(δ):15.3,(δ D):15.3,(δ P):0.0,(δ H):0.0) (a)-1 0.039質量份 (b)-1 3.883質量份 (c)-1 0.078質量份 (Example 1) After passing the release layer forming composition 1 of the following composition through a filter capable of removing more than 99% of foreign matter of 0.5 μm or more, it was coated using a reverse gravure so that the coating amount became 5.0 g/m 2 Apply on the surface layer A of the laminated film X1. Thereafter, the processing speed was adjusted so as to enter the first drying furnace after 0.5 seconds, and heating and drying were continuously performed at the first drying furnace temperature of 120°C and the second drying furnace temperature of 90°C. After the drying step, the cooling roll was irradiated with ultraviolet rays with a cumulative light intensity of 100 mJ/cm 2 by an ultraviolet irradiation machine (manufactured by Heraeus, H bulb) to harden the release layer to obtain a release film for resin sheet molding. In addition, as a result of evaluating the smoothness, peelability, and pinholes of the obtained release film, as shown in Table 1, favorable results were obtained. In this way, the obtained release film for resin sheet molding is a release film capable of producing, for example, a resin sheet having a thickness of 0.2 μm or more and 1.0 μm or less. In addition, the weight (mg/m 2 ) of each component (a), (b) and (c) described in the table represents the content ratio per unit solid content (the weight of each component relative to the total weight of the release layer). (Release layer forming composition 1) 24.000 parts by mass of methyl ethyl ketone (SP value (δ): 19.1, (δ D ): 16.0, (δ P ): 9.0, (δ H ): 5.1) 24.000 parts by mass of toluene Parts (SP value (δ): 18.2, (δ D ): 18.0, (δ P ): 1.4, (δ H ): 2.0) n-heptane 48.000 parts by mass (SP value (δ): 15.3, (δ D ) : 15.3, (δ P ): 0.0, (δ H ): 0.0) (a)-1 0.039 parts by mass (b)-1 3.883 parts by mass (c)-1 0.078 parts by mass
(實施例2至實施例4) 除了變更為表1所記載之離型層之組成、製造方法以外,利用和實施例1同樣的方法獲得了樹脂片成型用離型膜。 (Example 2 to Example 4) Except having changed the composition and manufacturing method of the release layer described in Table 1, the release film for resin sheet molding was obtained by the method similar to Example 1.
(實施例5) 除了使用下述組成之離型層形成組成物2以外,利用和實施例1同樣的方法獲得了樹脂片成型用離型膜。 (離型層形成組成物2) 甲基乙基酮 38.400質量份 (SP值(δ):19.1,(δ D):16.0,(δ P):9.0,(δ H):5.1) 甲苯 38.400質量份 (SP值(δ):18.2,(δ D):18.0,(δ P):1.4,(δ H):2.0) 正庚烷 19.200質量份 (SP值(δ):15.3,(δ D):15.3,(δ P):0.0,(δ H):0.0) (a)-1 0.196質量份 (b)-1 3.726質量份 (c)-1 0.078質量份 (Example 5) Except having used the release layer forming composition 2 of the following composition, the release film for resin sheet molding was obtained by the method similar to Example 1. (Release layer forming composition 2) 38.400 parts by mass of methyl ethyl ketone (SP value (δ): 19.1, (δ D ): 16.0, (δ P ): 9.0, (δ H ): 5.1) 38.400 parts by mass of toluene Parts (SP value (δ): 18.2, (δ D ): 18.0, (δ P ): 1.4, (δ H ): 2.0) n-heptane 19.200 parts by mass (SP value (δ): 15.3, (δ D ) : 15.3, (δ P ): 0.0, (δ H ): 0.0) (a)-1 0.196 parts by mass (b)-1 3.726 parts by mass (c)-1 0.078 parts by mass
(實施例6) 除了將離型層形成組成物中之正庚烷變更為環己烷(SP值(δ):16.8,(δ D):16.8,(δ P):0.0,(δ H):0.2)以外,利用和實施例2同樣的方法獲得了樹脂片成型用離型膜。 (Example 6) Except changing the n-heptane in the release layer forming composition to cyclohexane (SP value (δ): 16.8, (δ D ): 16.8, (δ P ): 0.0, (δ H ) : 0.2), the release film for resin sheet molding was obtained by the method similar to Example 2.
(實施例7、實施例8) 除了變更為表1所記載之塗布量與固形物比率以外,利用和實施例2同樣的方法獲得了樹脂片成型用離型膜。此時,以有機溶媒比率成為和離型層形成組成物1同樣的方式來進行製備。 (Example 7, Example 8) A release film for resin sheet molding was obtained in the same manner as in Example 2 except that the coating amount and the solid content ratio described in Table 1 were changed. At this time, it prepared so that the ratio of the organic solvent might become the same as that of the release layer forming composition 1.
(實施例9) 除了變更為以下組成之離型層形成用組成物3以外,利用和實施例1同樣的方法獲得了樹脂片成型用離型膜。 (離型層形成用組成物3) 甲基乙基酮 24.000質量份 (SP值(δ):19.1,(δ D):16.0,(δ P):9.0,(δ H):5.1) 甲苯 24.000質量份 (SP值(δ):18.2,(δ D):18.0,(δ P):1.4,(δ H):2.0) 正庚烷 48.000質量份 (SP值(δ):15.3,(δ D):15.3,(δ P):0.0,(δ H):0.0) (a)-1 0.039質量份 (b)-2 3.883質量份 (c)-1 0.078質量份 (Example 9) Except having changed into the composition 3 for release layer formation of the following composition, the release film for resin sheet molding was obtained by the method similar to Example 1. (Composition 3 for release layer formation) Methyl ethyl ketone 24.000 parts by mass (SP value (δ): 19.1, (δ D ): 16.0, (δ P ): 9.0, (δ H ): 5.1) Toluene 24.000 Parts by mass (SP value (δ): 18.2, (δ D ): 18.0, (δ P ): 1.4, (δ H ): 2.0) n-heptane 48.000 parts by mass (SP value (δ): 15.3, (δ D ): 15.3, (δ P ): 0.0, (δ H ): 0.0) (a)-1 0.039 parts by mass (b)-2 3.883 parts by mass (c)-1 0.078 parts by mass
(實施例10至實施例12) 除了變更為表1所記載之離型層之組成、製造方法以外,利用和實施例1同樣的方法獲得了樹脂片成型用離型膜。 (Example 10 to Example 12) Except having changed the composition and manufacturing method of the release layer described in Table 1, the release film for resin sheet molding was obtained by the method similar to Example 1.
(實施例13) 除了使用下述組成之離型層形成組成物4以外,利用和實施例1同樣的方法獲得了樹脂片成型用離型膜。 (離型層形成組成物4) 甲基乙基酮 38.400質量份 (SP值(δ):19.1,(δ D):16.0,(δ P):9.0,(δ H):5.1) 甲苯 38.400質量份 (SP值(δ):18.2,(δ D):18.0,(δ P):1.4,(δ H):2.0) 正庚烷 19.200質量 (SP值(δ):15.3,(δ D):15.3,(δ P):0.0,(δ H):0.0) (a)-1 0.196質量份 (b)-2 3.726質量份 (c)-1 0.078質量份 (Example 13) Except having used the release layer forming composition 4 of the following composition, the release film for resin sheet molding was obtained by the method similar to Example 1. (Release layer forming composition 4) 38.400 parts by mass of methyl ethyl ketone (SP value (δ): 19.1, (δ D ): 16.0, (δ P ): 9.0, (δ H ): 5.1) 38.400 parts by mass of toluene Parts (SP value (δ): 18.2, (δ D ): 18.0, (δ P ): 1.4, (δ H ): 2.0) n-heptane 19.200 mass (SP value (δ): 15.3, (δ D ): 15.3, (δ P ): 0.0, (δ H ): 0.0) (a)-1 0.196 parts by mass (b)-2 3.726 parts by mass (c)-1 0.078 parts by mass
(實施例14) 除了將離型層形成組成物中之正庚烷變更為環己烷(SP值(δ):16.8,(δ D):16.8,(δ P):0.0,(δ H):0.2)以外,利用和實施例2同樣的方法獲得了樹脂片成型用離型膜。 (Example 14) In addition to changing the n-heptane in the release layer forming composition to cyclohexane (SP value (δ): 16.8, (δ D ): 16.8, (δ P ): 0.0, (δ H ) : 0.2), the release film for resin sheet molding was obtained by the method similar to Example 2.
(實施例15、實施例16) 除了變更為表1所記載之塗布量與固形物比率以外,利用和實施例2同樣的方法獲得了樹脂片成型用離型膜。此時,以有機溶媒比率成為和離型層形成組成物3同樣的方式進行製備。 (Example 15, Example 16) A release film for resin sheet molding was obtained in the same manner as in Example 2 except that the coating amount and the solid content ratio described in Table 1 were changed. At this time, the organic solvent ratio was prepared in the same manner as that of the release layer forming composition 3 .
(實施例17) 除了使用下述組成之離型層形成用組成物5以外,利用和實施例1同樣的方法獲得了超薄層樹脂片成型用離型膜。 (離型層形成用組成物5) 甲基乙基酮 24.950質量份 (SP值(δ):19.1,(δ D):16.0,(δ P):9.0,(δ H):5.1) 甲苯 24.950質量份 (SP值(δ):18.2,(δ D):18.0,(δ P):1.4,(δ H):2.0) 正庚烷 49.900質量份 (SP值(δ):15.3,(δ D):15.3,(δ P):0.0,(δ H):0.0) (a)-1 0.196質量份 (c)-1 0.004質量份 (Example 17) Except having used the composition 5 for release layer formation of the following composition, the release film for ultrathin layer resin sheet molding was obtained by the method similar to Example 1. (Composition 5 for release layer formation) Methyl ethyl ketone 24.950 parts by mass (SP value (δ): 19.1, (δ D ): 16.0, (δ P ): 9.0, (δ H ): 5.1) Toluene 24.950 Parts by mass (SP value (δ): 18.2, (δ D ): 18.0, (δ P ): 1.4, (δ H ): 2.0) n-heptane 49.900 parts by mass (SP value (δ): 15.3, (δ D ): 15.3, (δ P ): 0.0, (δ H ): 0.0) (a)-1 0.196 parts by mass (c)-1 0.004 parts by mass
(實施例18) 除了變更為表1所記載之固形物濃度,並以有機溶媒比率成為和離型層形成組成物5同樣的方式進行製備以外,利用和實施例1同樣的方法獲得了樹脂片成型用離型膜。 (Example 18) A release film for resin sheet molding was obtained in the same manner as in Example 1, except that the concentration of the solid content described in Table 1 was changed to the organic solvent ratio and prepared in the same manner as the release layer forming composition 5. .
(實施例19) 除了變更為表1所記載之製造方法以外,利用和實施例17同樣的方法獲得了樹脂片成型用離型膜。 (Example 19) Except having changed into the manufacturing method described in Table 1, the release film for resin sheet molding was obtained by the method similar to Example 17.
(實施例20) 除了變更為離型層形成組成物6以外,利用和實施例1同樣的方法獲得了超薄層樹脂片成型用離型膜。 (離型層形成用組成物6) 甲基乙基酮 39.920質量份 (SP值(δ):19.1,(δ D):16.0,(δ P):9.0,(δ H):5.1) 甲苯 39.920質量份 (SP值(δ):19.1,(δ D):16.0,(δ P):9.0,(δ H):5.1) 正庚烷 19.960質量份 (SP值(δ):15.3,(δ D):15.3,(δ P):0.0,(δ H):0.0) (a)-1 0.196質量份 (c)-1 0.004質量份 (Example 20) Except having changed into the release layer forming composition 6, the release film for ultrathin layer resin sheet molding was obtained by the method similar to Example 1. (Composition 6 for release layer formation) Methyl ethyl ketone 39.920 parts by mass (SP value (δ): 19.1, (δ D ): 16.0, (δ P ): 9.0, (δ H ): 5.1) Toluene 39.920 Parts by mass (SP value (δ): 19.1, (δ D ): 16.0, (δ P ): 9.0, (δ H ): 5.1) n-heptane 19.960 parts by mass (SP value (δ): 15.3, (δ D ): 15.3, (δ P ): 0.0, (δ H ): 0.0) (a)-1 0.196 parts by mass (c)-1 0.004 parts by mass
(實施例21) 除了將離型層形成組成物5中之正庚烷變更為環己烷(SP值(δ):16.8,(δ D):16.8,(δ P):0.0,(δ H):0.2)以外,利用和實施例1同樣的方法獲得了樹脂片成型用離型膜。 (Example 21) In addition to changing the n-heptane in the release layer forming composition 5 to cyclohexane (SP value (δ): 16.8, (δ D ): 16.8, (δ P ): 0.0, (δ H ): 0.2) Except, the release film for resin sheet molding was obtained by the method similar to Example 1.
(實施例22、實施例23) 除了變更為表1所記載之塗布量、固形物濃度以外,利用和實施例17同樣的方法獲得了樹脂片成型用離型膜。此時,以有機溶媒比率成為和離型層形成組成物5同樣的方式進行了製備。 (Example 22, Example 23) A release film for resin sheet molding was obtained in the same manner as in Example 17 except that the coating amount and solid content concentration described in Table 1 were changed. At this time, the ratio of the organic solvent was prepared in the same manner as that of the release layer forming composition 5 .
(比較例1) 除了變更為下述組成之離型層形成組成物7以外,利用和實施例1同樣的方法獲得了超薄層樹脂片成型用離型膜。 (離型層形成組成物7) 甲基乙基酮 24.000質量份 (SP值(δ):19.1,(δ D):16.0,(δ P):9.0,(δ H):5.1) 甲苯 24.000質量份 (SP值(δ):18.2,(δ D):18.0,(δ P):1.4,(δ H):2.0) 正庚烷 48.000質量份 (SP值(δ):15.3,(δ D):15.3,(δ P):0.0,(δ H):0.0) (b)-1 3.922質量份 (c)-1 0.078質量份 (Comparative example 1) Except having changed into the release layer forming composition 7 of the following composition, the release film for ultrathin layer resin sheet molding was obtained by the method similar to Example 1. (Release layer forming composition 7) 24.000 parts by mass of methyl ethyl ketone (SP value (δ): 19.1, (δ D ): 16.0, (δ P ): 9.0, (δ H ): 5.1) 24.000 parts by mass of toluene Parts (SP value (δ): 18.2, (δ D ): 18.0, (δ P ): 1.4, (δ H ): 2.0) n-heptane 48.000 parts by mass (SP value (δ): 15.3, (δ D ) : 15.3, (δ P ): 0.0, (δ H ): 0.0) (b)-1 3.922 parts by mass (c)-1 0.078 parts by mass
(比較例2) 除了變更為下述組成之離型層形成組成物8以外,利用和實施例1同樣的方法獲得了超薄層樹脂片成型用離型膜。 (離型層形成組成物8) 甲基乙基酮 24.000質量份 (SP值(δ):19.1,(δ D):16.0,(δ P):9.0,(δ H):5.1) 甲苯 24.000質量份 (SP值(δ):18.2,(δ D):18.0,(δ P):1.4,(δ H):2.0) 正庚烷 48.000質量份 (SP值(δ):15.3,(δ D):15.3,(δ P):0.0,(δ H):0.0) (a)-1 2.941質量份 (b)-2 0.981質量份 (c)-1 0.078質量份 (Comparative example 2) Except having changed into the release layer forming composition 8 of the following composition, the release film for ultrathin layer resin sheet molding was obtained by the method similar to Example 1. (Release layer forming composition 8) 24.000 parts by mass of methyl ethyl ketone (SP value (δ): 19.1, (δ D ): 16.0, (δ P ): 9.0, (δ H ): 5.1) 24.000 parts by mass of toluene Parts (SP value (δ): 18.2, (δ D ): 18.0, (δ P ): 1.4, (δ H ): 2.0) n-heptane 48.000 parts by mass (SP value (δ): 15.3, (δ D ) : 15.3, (δ P ): 0.0, (δ H ): 0.0) (a)-1 2.941 parts by mass (b)-2 0.981 parts by mass (c)-1 0.078 parts by mass
(比較例3) 除了變更為下述組成之離型層形成組成物9以外,利用和實施例1同樣的方法獲得了超薄層樹脂片成型用離型膜。 (離型層形成組成物9) 甲基乙基酮 24.000質量份 (SP值(δ):19.1,(δ D):16.0,(δ P):9.0,(δ H):5.1) 甲苯 24.000質量份 (SP值(δ):18.2,(δ D):18.0,(δ P):1.4,(δ H):2.0) 正庚烷 48.000質量份 (SP值(δ):15.3,(δ D):15.3,(δ P):0.0,(δ H):0.0) (a)-1 3.922質量份 (c)-1 0.078質量份 (Comparative example 3) Except having changed into the release layer forming composition 9 of the following composition, the release film for ultrathin layer resin sheet molding was obtained by the method similar to Example 1. (Release layer forming composition 9) 24.000 parts by mass of methyl ethyl ketone (SP value (δ): 19.1, (δ D ): 16.0, (δ P ): 9.0, (δ H ): 5.1) 24.000 parts by mass of toluene Parts (SP value (δ): 18.2, (δ D ): 18.0, (δ P ): 1.4, (δ H ): 2.0) n-heptane 48.000 parts by mass (SP value (δ): 15.3, (δ D ) : 15.3, (δ P ): 0.0, (δ H ): 0.0) (a)-1 3.922 parts by mass (c)-1 0.078 parts by mass
(比較例4) 除了塗布於積層膜X2以外,利用和實施例10同樣的方法獲得了超薄層樹脂片成型用離型膜。 (comparative example 4) A release film for forming an ultra-thin layer resin sheet was obtained in the same manner as in Example 10 except for coating on the laminated film X2.
[表1A]
[表1B]
[表1C]
[表2A]
[表2B]
[表2C]
比較例1由於不含陽離子硬化型聚二甲基矽氧烷(a),故陶瓷片之剝離力大,剝離為不可能。比較例2至比較例4,高度10nm以上之突起數超過200個/mm 2,於被離型物之生坯產生了針孔。進而比較例4於基材全體存在有無機粒子,離型膜之平滑性顯著差,產生了生坯之破損、針孔等。 [產業可利用性] Since Comparative Example 1 does not contain cation-curable polydimethylsiloxane (a), the peeling force of the ceramic sheet is large and peeling is impossible. In Comparative Example 2 to Comparative Example 4, the number of protrusions with a height of 10 nm or more exceeded 200/mm 2 , and pinholes were formed in the green body of the to-be-released object. Furthermore, in Comparative Example 4, inorganic particles existed in the entire substrate, and the smoothness of the release film was remarkably poor, and breakage, pinholes, etc. of the green sheet occurred. [Industrial availability]
依據本發明,藉由提高離型層之平滑性與剝離性,可提供一種離型膜,即便是厚度為1μm以下的超薄層品仍可成型出少有缺陷的樹脂片,從而可不用擔心發生不良來製造樹脂片。According to the present invention, by improving the smoothness and detachability of the release layer, a release film can be provided. Even an ultra-thin laminate with a thickness of less than 1 μm can still be molded into a resin sheet with few defects, so that there is no need to worry about it. Defects occur to manufacture resin sheets.
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