CN103764710B - Resin film - Google Patents
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- CN103764710B CN103764710B CN201280041955.0A CN201280041955A CN103764710B CN 103764710 B CN103764710 B CN 103764710B CN 201280041955 A CN201280041955 A CN 201280041955A CN 103764710 B CN103764710 B CN 103764710B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4078—Curing agents not provided for by the groups C08G59/42 - C08G59/66 boron containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
The invention provides a kind of resin film being suitable as sacrifice layer and using in MEMS technology field.The present invention a kind of is 40 ~ 80 DEG C by (A) second-order transition temperature (Tg) and the resin film having that the acrylic resin of the functional group reacted with epoxy resin, (B) epoxy resin, (C) phenol resins and (D) tetraphenylphosphoniphenolate four (p-methylphenyl) borate form.
Description
Technical field
The present invention is about a kind of resin film, and it is in MEMS (MicroElectroMechanicalSystem) technical field, when manufacture has the micro architecture body of hollow structure, is suitable as sacrifice layer and uses.
Background technology
On the semiconductor substrates such as such as silicon or on the insulator substrate such as glass or the fine structure of the first-class making of metal MEMS technology at present just under development.
In MEMS technology field, usually use sacrifice layer when manufacturing and there is the micro architecture body of hollow structure.Such as by forming sacrifice layer between upper/lower electrode layer, then optionally removing sacrifice layer, can be formed and be configured to spaced two electrode structures (with reference to patent documentation 1,2) each other.
As sacrifice layer used for this purpose, from can film forming and the reason such as patterning can be carried out easily consider at low temperatures, have the situation adopting organic resin.Such as, in patent documentation 1, use polyimide resin, BCB resin, fluoro-resin, polyamide resin etc. organic resin is described.
Form sacrifice layer by coating method in patent documentation 1, and from easily forming the uniform sacrifice layer of thickness and the number of steps reason such as to tail off is considered when forming sacrifice layer, adopt the position for forming sacrifice layer to have the resin film of adherence to form the situation of sacrifice layer advantageously.
In addition, in patent documentation 1,2, also describe ashing method, such as, carry out ashing by oxygen plasma or carry out ashing etc. by being exposed to ozone environment to sacrifice layer heating simultaneously.But in these methods, be necessary the residue after removing ashing.
Concerning this point, if sacrifice layer can be dissolved removing by solvent etc., then can not remain after removal of the sacrificial layer, comparatively applicable.
Semi-conductor uses then film to have the possibility of the sacrifice layer used as such use.
As semi-conductor then film, there will be a known the product such as described in patent documentation 3,4.
But, the then film of the semi-conductor described in patent documentation 3,4.The second-order transition temperature (Tg) of acrylic copolymer contained in its composition is low, and the normal temperature therefore below 30 DEG C can stick.Therefore, when film being placed in the position forming film and sacrifice layer, be difficult to the bubble removing that will be present between the two.When carrying out thermo-compressed by calendering under gas bubbles left state between, during thermo-compressed, bubble can expand, and therefore has the misgivings that the stripping of sacrifice layer or position skew occur.
In addition; commissure is attached in order to prevent foreign matter; then film before using preserves under the state sandwiched by the protective film such as polyethylene terephthalate (PET) film, if but present at then film and stick, then become and be difficult to then film to be separated from protective film.
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-83881 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2010-214480 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2002-180021 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2006-182919 publication
Summary of the invention
The problem that invention will solve
The present invention is in order to solve the problem in above-mentioned prior art, and object is to provide a kind of resin film being suitable as sacrifice layer and using in MEMS technology field.
The characteristic possessed needed for this resin film is as follows:
. can not stick under the normal temperature below 30 DEG C.
. excellent by the adherence of rolling when carrying out thermo-compressed.
. when carrying out thermo-compressed by calendering, dimensional change is little.
. excellent in workability when being undertaken patterning by laser.
. resistance to plating is excellent.
. the film after heat hardening and after processing removes by organic solvent dissolution.
For the means of dealing with problems
In order to reach above-mentioned purpose, the invention provides a kind of resin film, this resin film is 40 ~ 80 DEG C by (A) second-order transition temperature (Tg) and has the acrylic resin of the functional group reacted with epoxy resin, (B) epoxy resin, (C) phenol resins and (D) tetraphenylphosphoniphenolate four (p-methylphenyl) borate to form.
In resin film of the present invention, described (A) acrylic resin is to have hydroxyl as the functional group reacted with described epoxy resin for good.
In resin film of the present invention, the hydroxyl valency of described (A) acrylic resin with 1 ~ 30 [mg/KOH] for good.
In resin film of the present invention, described (A) acrylic resin is to have carboxyl as the functional group reacted with described epoxy resin for good.
In resin film of the present invention, the carboxyl equivalent of described (A) acrylic resin is with 1,300g/eq ~ 39, and 000g/eq is good.
In resin film of the present invention, the weight-average molecular weight (Mw) of described (A) acrylic resin is with 300, and 000 ~ 800,000 is good.
In resin film of the present invention, described (B) epoxy resin is good with at least one in the group being selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, biphenyl type epoxy resin and aliphatics type epoxy resin and being formed.
In resin film of the present invention, described (B) epoxy resin is better with bisphenol A type epoxy resin.
In resin film of the present invention, the content of described (B) epoxy resin, relative to described (A) acrylic resin 100 mass parts, is good with 5 ~ 50 mass parts.
In resin film of the present invention, described (C) phenol resins is good with at least one in the group being selected from terpene phenol resin, bisphenol A-type phenol resins, bisphenol-f type phenol resins and novolac type phenol resin and being formed.
In resin film of the present invention, described (C) phenol resins is better with terpene phenol resin.
In resin film of the present invention, the content of described (C) phenol resins, relative to (A) acrylic resin 100 mass parts, is good with 10 ~ 35 mass parts.
The effect of invention
Resin film of the present invention meets for the characteristic required by the resin film as above-mentioned sacrifice layer.Therefore, be suitable as sacrifice layer to use in MEMS technology field.
Embodiment
Elaborate for the present invention below.
Resin film of the present invention is made up of (A) shown below ~ (D) composition.
(A) composition: acrylic resin
(A) acrylic resin of composition is in resin film of the present invention, for contributing to flexibility and the composition by rolling dimensional stability when carrying out thermo-compressed.In addition, when manufacturing resin film, the intermiscibility with other compositions is contributed to.
(A) acrylic resin of composition when the heat hardening of resin film, must react with the epoxy resin of (B) composition.Therefore, as the acrylic resin of (A) composition, adopt the material with the functional group that can react with epoxy resin.
As the functional group that can react with epoxy resin, when using tetraphenylphosphoniphenolate four (p-methylphenyl) borate as the hardening accelerator of epoxy resin, it seems from the viewpoint good with the reaction of epoxy resin, is good with hydroxyl and carboxyl.
Hydroxyl wherein, when using tetraphenylphosphoniphenolate four (p-methylphenyl) borate as the hardening accelerator of epoxy resin, it seems as better from the viewpoint that the reaction with epoxy resin is good especially.
When the acrylic resin of (A) composition has hydroxyl as the functional group that can react with epoxy resin, the hydroxyl valency of acrylic resin with 1 ~ 30 [mg/KOH] for good.If the hydroxyl valency of acrylic resin is less than 1 [mg/KOH], then can not occurs with the reaction of epoxy resin, have the misgivings that cannot obtain sufficient adhesion.On the other hand, if the hydroxyl valency of acrylic resin is greater than 30 [mg/KOH], then carry out with the overreact of epoxy resin, cross-linking density uprises, and has the misgivings by organic solvent, the resin film after heat hardening cannot being dissolved removing.
The hydroxyl valency of acrylic resin is better with 5 ~ 20 [mg/KOH], is better with 10 ~ 15 [mg/KOH].
When the acrylic resin of (A) composition has carboxyl as the functional group that can react with epoxy resin, the carboxyl equivalent of acrylic resin is with 1,300g/eq ~ 39, and 000g/eq is good.If the carboxyl equivalent of acrylic resin is greater than 39,000g/eq, then can not occurs with the reaction of epoxy resin, have the misgivings that cannot obtain enough adhesions.On the other hand, if the carboxyl equivalent of acrylic resin is less than 1,300g/eq, then carry out with the overreact of epoxy resin, cross-linking density uprises, and has the misgivings by organic solvent, the resin film after heat hardening cannot being dissolved removing.
The carboxyl equivalent of acrylic resin is with 2,000g/eq ~ 8, and 000g/eq is better, and with 2,600g/eq ~ 4,000g/eq is better.
(A) second-order transition temperature (Tg) of the acrylic resin of composition is 40 ~ 80 DEG C.
As long as the Tg of acrylic resin is at 40 ~ 80 DEG C, then resin film presents the temperature that sticks and can appropriateness uprise, and under the normal temperature therefore less than 30 DEG C, can not present stick when resin film being placed in the position of formation sacrifice layer.So, when resin film being placed in the position forming sacrifice layer, even if there is bubble to be present between the two, also can easily bubble be removed.Therefore, under state between the two, carry out thermo-compressed at gas bubbles left by calendering, the misgivings that the stripping of sacrifice layer or position skew occur are solved.In addition also easy by use before resin film be separated from protective film.
It is more than 40 DEG C that resin film of the present invention presents the temperature sticked, and is preferably 40 ~ 80 DEG C, is preferably 50 ~ 70 DEG C, is more preferred from 50 ~ 60 DEG C.
So resin film presents the temperature sticked can not become high, be therefore suitable for carrying out thermo-compressed by calendering and forming sacrifice layer.
In addition, in this manual present the temperature sticked, mean, when being sticked method by probe and measuring, to present temperature during the sticking of more than 0.1N.
If the Tg of acrylic resin is less than 40 DEG C, then cannot giving full play of the effect presenting the temperature sticked improving resin film, the normal temperature below 30 DEG C, when resin film being placed in the position forming sacrifice layer, having the misgivings presenting and stick.In addition, become large by the dimensional change of rolling when carrying out thermo-compressed.On the other hand, if the Tg of acrylic resin is more than 80 DEG C, then resin film presents the temperature sticked and becomes high, is difficult to carry out thermo-compressed by calendering and form sacrifice layer.In addition, can reduce with the intermiscibility of other compositions, workability when manufacturing resin film worsens.In addition, resin film flexibility is poor.
The Tg of acrylic resin is good with 45 ~ 60 DEG C.
As composition (A) as long as the acrylic resin adopted has the functional group that can react with epoxy resin, and Tg is 40 ~ 80 DEG C, then and be not particularly limited, be good with the methyl methacrylate butyl acrylate copolymer containing methyl methacrylate composition and butyl acrylate composition.In addition, when being used alone these compositions forming multipolymer, the effect wishing to reach cannot have been given play to.When being used alone methyl methacrylate composition, the flexibility of film is poor, when being used alone butyl acrylate composition, has nothing to do with Tg, and can present under normal temperature below 30 DEG C and stick.
Wherein, from the resin film being easier to obtain to present the temperature that sticks and being controlled, and the viewpoint of film flexibility excellence be it seems, it is good for containing methyl methacrylate composition (x) with the methyl methacrylate butyl acrylate copolymer of butyl acrylate composition (y) with the ratio of x/y=8/2 ~ 6/4.If x/y > 8/2, then have the tendency of film flexibility difference, if x/y < 6/4, then become and be difficult to control film by the Tg of acrylic resin and present the temperature sticked.
In addition, it seems from the viewpoint kept with the intermiscibility of other compositions and the layer insulation of film, methyl methacrylate butyl acrylate copolymer meet above-mentioned scope with x/y and weight-average molecular weight (Mw) for 300,000 ~ 800,000 is good.
At Mw less than 300, when 000, have the misgivings of the layer insulation that cannot keep film.On the other hand, at Mw more than 800, when 000, reduce with the intermiscibility of other compositions, therefore have the misgivings becoming and be difficult to manufacture film.
The weight-average molecular weight (Mw) of methyl methacrylate butyl acrylate copolymer is with 400, and 000 ~ 700,000 is better, and with 450,000 ~ 600,000 is better.
(B) composition: epoxy resin
(B) epoxy resin of composition is contribute to the thermosetting of resin film of the present invention and the composition of adherence.
(B) epoxy resin that adopts of composition being not particularly limited, can use various epoxy resin.It seems from excellent viewpoints such as the dependencys of Bonding strength and thermotolerance, epoxy resin is good with bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, biphenyl type epoxy resin, aliphatics type epoxy resin.
In addition, any one in above-mentioned epoxy resin can be used, also can be used together two or more.
It seems from viewpoints excellent especially such as the dependencys of Bonding strength and thermotolerance, being better with bisphenol A type epoxy resin, bisphenol f type epoxy resin in above-mentioned epoxy resin, is better with bisphenol A type epoxy resin.
Consider from reasons such as reactivity, adhesion, solvabilities, the epoxy resin that (B) composition adopts is with weight-average molecular weight (Mw) for 100 ~ 5, and 000 is good.
The weight-average molecular weight (Mw) of epoxy resin is with 200 ~ 2, and 000 is better, and with 300 ~ 1,000 is better.
In resin film of the present invention, the content of the epoxy resin of (B) composition, relative to acrylic resin 100 mass parts of (A) composition, is good with 5 ~ 50 mass parts.
If (B) content of the epoxy resin of composition is less than 5 mass parts, then have the misgivings that Bonding strength becomes not enough.On the other hand, if the content of the epoxy resin of (B) composition is more than 50 mass parts, then becomes and be difficult to adjust with the intermiscibility of other compositions or present the temperature sticked.In addition, become large by the dimensional change of rolling when carrying out thermo-compressed.
(B) content of the epoxy resin of composition is relative to acrylic resin 100 mass parts of (A) composition, and being better with 30 ~ 50 mass parts, is better with 35 ~ 45 mass parts.
(C) composition: phenol resins
(C) phenol resins of composition can be used as the stiffening agent of the tackiness imparting agent of resin film of the present invention and the epoxy resin of (B) composition and plays a role.In addition, when manufacturing resin film, the intermiscibility with other compositions is contributed to.
(C) phenol resins that adopts of composition being not particularly limited, can use various phenol resins.It seems from the tackiness of resin film and the viewpoint of adherence excellence, phenol resins is good with terpene phenol resin, bisphenol A-type phenol resins, bisphenol-f type phenol resins, novolac type phenol resin.
In addition, any one in above-mentioned phenol resins can be used, also can be used together two or more.
It seems from the tackiness of resin film and the excellent especially viewpoint of adherence, is better with terpene phenol resin in above-mentioned phenol resins.
In resin film of the present invention, the content of the phenol resins of (C) composition, relative to acrylic resin 100 mass parts of (A) composition, is good with 10 ~ 35 mass parts.
If (C) content of the phenol resins of composition is less than 10 mass parts, then have the misgivings that Bonding strength becomes not enough.On the other hand, if the content of the phenol resins of (C) composition is more than 30 mass parts, then becomes and be difficult to adjust the intermiscibility with other compositions.
(C) content of the phenol resins of composition, relative to acrylic resin 100 mass parts of (A) composition, being better with 10 ~ 30 mass parts, is better with 15 ~ 25 mass parts.
(D) composition: tetraphenylphosphoniphenolate four (p-methylphenyl) borate
(D) tetraphenylphosphoniphenolate four (p-methylphenyl) borate of composition can in then film of the present invention, as the epoxy resin of (B) composition hardening accelerator and play a role.
If the hardening accelerator of epoxy resin adopts general imidazoles, then between epoxy resin, sclerous reaction occurs, and formed three-dimensional cross-linked, therefore cross-linking density uprises, and by organic solvent, the resin film after heat hardening cannot be dissolved removing.
On the other hand, if (D) tetraphenylphosphoniphenolate four (p-methylphenyl) borate of composition uses together with the phenol resins of (C) composition, sclerous reaction then between the epoxy resin of (B) composition can not be carried out, between the heterogeneity contained by resin film, namely between the acrylic resin and the epoxy resin of (B) composition of (A) composition, (A) between the acrylic resin of composition and the phenol resins of (C) composition, or can sclerous reaction be there is between the phenol resins of the epoxy resin of (B) composition and (C) composition, therefore cross-linking density can not uprise, and by organic solvent, the resin film after heat hardening can be dissolved removing.
In resin film of the present invention, tetraphenylphosphoniphenolate four (p-methylphenyl) the boratory content of (D) composition, relative to acrylic resin 100 mass parts of (A) composition, is good with 0.1 ~ 5 mass parts.
If (D) tetraphenylphosphoniphenolate four (p-methylphenyl) the borate content of composition is less than 0.1 mass parts, then the sclerous reaction of epoxy resin can not be carried out, and has and cause then hypodynamic misgivings because of under-ageing.On the other hand.If (D) tetraphenylphosphoniphenolate four (p-methylphenyl) the borate content of composition is more than 5 mass parts, then the sclerous reaction of epoxy resin is carried out too fast, therefore, when using resin film of the present invention as the sacrifice layer used when manufacturing and have the micro architecture body of hollow structure, the misgivings becoming and be difficult to show in concavo-convex the problems such as imbedibility and occur are had.
(D) tetraphenylphosphoniphenolate four (p-methylphenyl) the boratory content of composition, relative to acrylic resin 100 mass parts of (A) composition, being better with 0.1 ~ 3 mass parts, is better with 0.1 ~ 2 mass parts.
The thickness of resin film of the present invention is good with 5 ~ 50 μm.If the thickness of resin film is more than 50 μm, then thickness is too thick, and therefore the flexibility of film reduces, and operability worsens.In addition, because bubble is involved in or residual the causing of solvent produces bubble etc. in subsequent step, and manufactured film is made easily to have gas bubbles left.In addition, be difficult to produce the uniform film of composition.On the other hand, if the thickness of film is less than 5 μm, then thickness is too thin, therefore has the misgivings that film splits then time or when operating.Also become easy static electrification in addition, therefore operability worsens.
The thickness of resin film of the present invention is better with 10 ~ 40 μm, is better with 10 ~ 35 μm.
Resin film of the present invention is by being dissolved or dispersed in solvent with desired containing proportional composition (A) ~ (D) that make, by obtained solution coat after base material, solvent is removed by base material heating, then obtains from base material removing.
Now used solvent can enumerate the lower methyl ethyl ketone of boiling point, acetone, methyl iso-butyl ketone (MIBK), toluene, ethylene glycol butyl ether, cellosolvo, methyl alcohol, ethanol, Virahol etc.
Base material can adopt the acrylic resin different base material be inclined to each other of hydrophobicity or wetting ability and (A) composition.The acrylic resin different base material be inclined to each other of hydrophobicity or wetting ability and (A) composition, the applicable base material adopting high molecular film material or the inorganic materials obtained at the coating drying compositions such as polyimide, glass, polypropylene or polyethylene terephthalate or hydrophobic ingredient.
In order to prevent foreign matter from adhering to, the resin film of the present invention before using is preserved under the state sandwiched by protective film.Protective film can adopt as the material described in base material.
Resin film of the present invention has the characteristic being suitable as sacrifice layer and using in MEMS technology field.
As mentioned above, the normal temperature of resin film of the present invention below 30 DEG C can not present and sticks, and the temperature more than 50 DEG C can present and sticks.So, when resin film being placed in the position forming sacrifice layer, even if there is bubble to be present between the two, also can easily bubble be removed.Therefore under gas bubbles left state between, carry out thermo-compressed by calendering, the misgivings that the stripping of sacrifice layer or position skew occur are solved.In addition, easily the resin film before use is separated from protective film.In addition, resin film presents the temperature sticked can not become high, is therefore adapted to pass through calendering and carries out thermo-compressed and form sacrifice layer.
Resin film of the present invention can temperature hardened more than 150 DEG C, and adhesion is increased.
When using resin film of the present invention to form sacrifice layer, resin film is placed in side in the position forming sacrifice layer and (namely sandwiches sacrifice layer and in the integrant of overlying relation each other, the integrant of below) time, as long as (that is sandwich sacrifice layer and in the integrant of overlying relation each other loading into the opposite side in the position making formation sacrifice layer, the integrant of top) under the state that connects with the exposed surface of resin film, thermo-compressed is carried out by calendering with determined temperature and given time, specifically for carry out thermo-compressed 60 ~ 90 minutes at 150 DEG C.In addition, when carrying out thermo-compressed by calendering, resin film of the present invention can heat hardening.Below, in this manual, the characteristic of the resin film of the present invention after thermo-compressed is recited as the resin film characteristic after heat hardening.
The dimensional change of resin film of the present invention when being carried out thermo-compressed by calendering is little.Specifically, according to described in aftermentioned embodiment sequentially pass through calendering carry out thermo-compressed and measure resin film variation in thickness time, measured resin film variation in thickness, less than 10 μm, is preferably less than 5 μm, is preferably less than 2 μm, is more preferred from less than 1 μm.
Resin film of the present invention after heat hardening has sufficient Bonding strength.Specifically, be more than 0.2N/cm according to the stripping strength measured by JISC5416, be preferably more than 0.4N/cm, be preferably more than 1.0N/cm.
Resin film of the present invention after heat hardening dissolves removing by selecting suitable organic solvent.With regard to the organic solvent that this object uses, ketone series solvent can enumerate acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), DIBK (diisobutyl ketone), pimelinketone, DAA (diacetone alcohol) etc.; Hydrocarbon system solvent can enumerate toluene, dimethylbenzene, solvent oil, normal hexane, isohexane, hexanaphthene, methylcyclohexane etc.Excellent from solvability, can carry out dry viewpoint at low temperature, be wherein good with methyl ethyl ketone, acetone.
In addition, the resin film of the present invention after heat hardening, processibility when it is undertaken patterning by laser and resistance to plating excellence.
Embodiment
(example 1 ~ 39)
Following, example 1 ~ 15,24 ~ 39 is embodiment, example 16 ~ 23 is comparative example.
The mix proportions (mass parts) disclosed with table 1 ~ 6 makes composition (A) ~ (D) be dissolved in solvent (methyl ethyl ketone), by obtained solution coat after base material (PET film through release process), to base material heating to remove desolventizing, then removed by base material, obtain resin film (thickness 30 μm) by this.
In addition, composition (A) ~ (D) is as described below respectively.
composition (A)
Acrylic resin A1: methyl methacrylate butyl acrylate copolymer (ratio=7/3, Tg:50 DEG C, Mw:500,000, functional group: hydroxyl, hydroxyl valency: 10 [mg/KOH])
Acrylic resin A2: methyl methacrylate butyl acrylate copolymer (ratio=7/3, Tg:50 DEG C, Mw:510,000, functional group: hydroxyl, hydroxyl valency: 1 [mg/KOH])
Acrylic resin A3: methyl methacrylate butyl acrylate copolymer (ratio=4/6, Tg:20 DEG C, Mw:650,000, functional group: hydroxyl, hydroxyl valency: 10 [mg/KOH])
Acrylic resin A4: methyl methacrylate butyl acrylate copolymer (ratio=2/8, Tg:-30 DEG C, Mw:800,000, functional group: hydroxyl, hydroxyl valency: 10 [mg/KOH])
Acrylic resin A5: methyl methacrylate butyl acrylate copolymer (ratio=8/2, Tg:90 DEG C, Mw:400,000, functional group: hydroxyl, hydroxyl valency: 10 [mg/KOH])
Acrylic resin A6: methyl methacrylate butyl acrylate copolymer (ratio=7/3, Tg:50 DEG C, Mw:550,000, hydroxyl valency: 30 [mg/KOH])
Acrylic resin A7: methyl methacrylate butyl acrylate copolymer (ratio=7/3, Tg:50 DEG C, Mw:500,000, functional group: carboxyl, carboxyl equivalent: 3,900 [g/eq])
Acrylic resin a: methyl methacrylate (Tg:120 DEG C, Mw:18,000, hydroxyl valency: 150 [mg/KOH])
composition (B)
Epoxy resin B1: bisphenol A type epoxy resin (Mw:370)
Epoxy resin B2: bisphenol f type epoxy resin (Mw:340)
Epoxy resin B3: phenol aldehyde type epoxy resin (Mw:360)
Epoxy resin B4: biphenyl type epoxy resin (Mw:550)
Epoxy resin B5: aliphatics type epoxy resin (Mw:290)
composition (C)
Phenol resins C1: terpene phenol resin (Mw:1100, hydroxyl valency: 50 [mg/KOH])
Phenol resins C2: terpene phenol resin (Mw:700, hydroxyl valency: 35 [mg/KOH])
Phenol resins C3: bisphenol A-type phenol resins (Mw:330, hydroxyl valency: 330 [mg/KOH])
Phenol resins C4: bisphenol-f type phenol resins (Mw:100, hydroxyl valency: 390 [mg/KOH])
Phenol resins C5: novolac type phenol resin (Mw:400, hydroxyl valency: 370 [mg/KOH])
composition (D)
Sclerosis catalyst D: tetraphenylphosphoniphenolate four (p-methylphenyl) borate
Sclerosis catalyst d1: imidazoles
Sclerosis catalyst d2: tetraphenylphosphoniphenolate tetraphenyl borate salts
Sclerosis catalyst d3: triphenyl phosphine
For obtained resin film or make the solution before resin film, implement the assessment of following physical property.
intermiscibility
The solution stirring that composition (A) ~ (D) will be made to be dissolved in obtain in solvent (methyl ethyl ketone), to evenly, then by following benchmark, is assessed for the solution after leaving standstill.
Zero: be uniform state when at room temperature standing solution after 1 week is visual.
△: be uneven state when at room temperature standing solution after 2 days is visual.
×: even if stir still uneven.
filming
Filming is assessed by following benchmark.
Zero: when making resin film according to said sequence, uniform film can be obtained.
×: when making resin film according to said sequence, cannot filming.
Be stained with glutinous: use probe to stick test machine and with 60 DEG C, sticking of resin film surface is measured at 25 DEG C.
Solvability: making resin film 150 DEG C of heat hardenings, after 60 minutes, makes it be dissolved in organic solvent (methyl ethyl ketone).Assessed by following benchmark.
Zero: be dissolved in organic solvent completely.
×: swelling is not still dissolved.
Bonding strength: by calendering by resin film and Copper Foil (thickness 18 μm) thermo-compressed: (150 DEG C, 60 minutes, 0.5MPa), after making laminate, be cut into the testing plate of width 10mm.And the intensity measured when Copper Foil being torn with 180 °.
Variation in thickness during thermo-compressed: according to said sequence by calendering by resin film and Copper Foil thermo-compressed time, mensuration resin film variation in thickness.
Result is disclosed in table 1 ~ 6.
[table 1]
[table 2]
[table 3]
[table 4]
[table 5]
[table 6]
Aobvious from showing, be in the example 1 ~ 15,24 ~ 39 of the acrylic resin (A1, A2, A6, A7) of 50 DEG C at employing Tg, (25 DEG C) can not present in fact and stick at normal temperatures.Particularly relative to the acrylic resin of 100 mass parts (A) composition, the sticking property of the example 1 ~ 6,8 ~ 15,24 ~ 39 of the epoxy resin containing (B) below 50 mass parts composition (25 DEG C) is at normal temperatures excellent especially.On the other hand, adopting in the example 16 ~ 17 of Tg less than the acrylic resin (A3, A4) of 50 DEG C (20 DEG C ,-30 DEG C), (25 DEG C) can present and stick at normal temperatures.On the other hand, Tg is being adopted to be that in the example 18 of acrylic resin (A5) of 90 DEG C, intermiscibility is poor, cannot filming.In addition, use Tg be the acrylic resin a of 120 DEG C example 19 due to intermiscibility poor, therefore do not implement filming.
The sclerosis catalyst of composition (D) adopts tetraphenylphosphoniphenolate four (p-methylphenyl) boratory example 1 ~ 15,24 ~ 39, and any one all makes the resin film after heat hardening dissolve by organic solvent.On the other hand, the catalyst that hardens adopts the example 20 of imidazoles the resin film after heat hardening cannot be dissolved by organic solvent.In addition, sclerosis catalyst adopts the example 19 of tetraphenylphosphoniphenolate tetraphenyl borate salts, adopts example 20 intermiscibility of triphenylphosphine poor, does not therefore implement filming.
In example 1 ~ 15,24 ~ 39, any one is all excellent by the Bonding strength rolled when carrying out thermo-compressed.
In addition, example 1 ~ 15,24 ~ 39 is when carrying out thermo-compressed by calendering, and all resin film variation in thickness is little for any one.On the other hand, in the example 16 ~ 17 using Tg less than the acrylic resin (A3, A4) of 50 DEG C (20 DEG C ,-30 DEG C), large by the resin film variation in thickness of rolling when carrying out thermo-compressed.
In addition, not containing the acrylic resin of (A) composition example 23 at normal temperatures (25 DEG C) can present and stick, resin film variation in thickness when carrying out thermo-compressed by calendering is also very large.
In addition, in the acrylic resin of (A) composition, the functional group reacted with epoxy resin be hydroxyl or carboxyl when all show good physical property (variation in thickness when Bonding strength when solvability after intermiscibility, filming, sticking property, heat hardening, thermo-compressed, thermo-compressed).
In addition, (B) epoxy resin of composition adopts bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, biphenyl type epoxy resin, the situation of any one of aliphatics type epoxy resin all shows good physical property (intermiscibility, filming, sticking property, solvability after heat hardening, Bonding strength during thermo-compressed, variation in thickness during thermo-compressed), (C) phenol resins of composition adopts terpene phenol resin, bisphenol A-type phenol resins, bisphenol-f type phenol resins, the situation of any one of novolac type phenol resin all shows good physical property (intermiscibility, filming, sticking property, solvability after heat hardening, Bonding strength during thermo-compressed, variation in thickness during thermo-compressed).
Claims (7)
1. a resin film, is 40 ~ 80 DEG C by (A) second-order transition temperature (Tg) and has the acrylic resin of the functional group reacted with epoxy resin, (B) epoxy resin, (C) phenol resins and (D) tetraphenylphosphoniphenolate four (p-methylphenyl) borate to form; Wherein, (A) acrylic resin is the methyl methacrylate butyl acrylate copolymer containing methyl methacrylate composition (x) and butyl acrylate composition (y) with the ratio of x/y=8/2 ~ 6/4, described (A) acrylic resin has hydroxyl as the functional group reacted with described epoxy resin, and hydroxyl valency is 1 ~ 30mg/KOH.
2. a resin film, is 40 ~ 80 DEG C by (A) second-order transition temperature (Tg) and has the acrylic resin of the functional group reacted with epoxy resin, (B) epoxy resin, (C) phenol resins and (D) tetraphenylphosphoniphenolate four (p-methylphenyl) borate to form; Wherein, (A) acrylic resin is the methyl methacrylate butyl acrylate copolymer containing methyl methacrylate composition (x) and butyl acrylate composition (y) with the ratio of x/y=8/2 ~ 6/4, described (A) acrylic resin has carboxyl as the functional group reacted with described epoxy resin, carboxyl equivalent is l, 300g/eq ~ 39,000g/eq.
3., according to the resin film that claim 1 or 2 is recorded, wherein, the weight-average molecular weight (Mw) of described (A) acrylic resin is 300,000 ~ 800,000.
4. according to the resin film that claim 1 or 2 is recorded, wherein, described (B) epoxy resin is at least one in the group that is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, biphenyl type epoxy resin and aliphatics type epoxy resin and forms.
5., according to the resin film that claim 1 or 2 is recorded, wherein, relative to described (A) acrylic resin 100 mass parts, the content of described (B) epoxy resin is 5 ~ 50 mass parts.
6. according to the resin film that claim 1 or 2 is recorded, wherein, described (C) phenol resins is for being selected from least one in the group that is made up of terpene phenol resin, bisphenol A-type phenol resins, bisphenol-f type phenol resins and novolac type phenol resin.
7., according to the resin film that claim 1 or 2 is recorded, wherein, relative to described (A) acrylic resin 100 mass parts, the content of described (C) phenol resins is 10 ~ 35 mass parts.
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| JP2011-195596 | 2011-09-08 | ||
| JP2011195596A JP4944269B1 (en) | 2011-09-08 | 2011-09-08 | Resin film |
| PCT/JP2012/052235 WO2013035350A1 (en) | 2011-09-08 | 2012-02-01 | Resin film |
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| KR (1) | KR101840087B1 (en) |
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| JP2015139925A (en) * | 2014-01-28 | 2015-08-03 | 三菱樹脂株式会社 | laminated polyester film |
| CN104877308B (en) * | 2015-05-11 | 2017-06-20 | 江苏江城电气有限公司 | A kind of wind power pipe bus special isolation film |
| JP6217711B2 (en) | 2015-08-21 | 2017-10-25 | 日亜化学工業株式会社 | Method for manufacturing light emitting device |
| JP6288009B2 (en) | 2015-08-31 | 2018-03-07 | 日亜化学工業株式会社 | Method for manufacturing light emitting device |
| JP6867575B2 (en) * | 2017-05-24 | 2021-04-28 | ナミックス株式会社 | Resin compositions, backgrind films, and cured products thereof |
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| CN101307221A (en) * | 2007-05-17 | 2008-11-19 | 日东电工株式会社 | Thermosetting encapsulation adhesive sheet |
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| JP2006182919A (en) * | 2004-12-28 | 2006-07-13 | Sumitomo Bakelite Co Ltd | Adhesive film for semiconductor and semiconductor device using the same |
| JP2006199812A (en) * | 2005-01-20 | 2006-08-03 | Nichias Corp | Conductive epoxy resin composition and separator for fuel cell |
| JP5805925B2 (en) * | 2008-10-02 | 2015-11-10 | 日立化成株式会社 | Die bonding film and semiconductor device using the same |
| JP5263134B2 (en) * | 2009-12-07 | 2013-08-14 | 住友ベークライト株式会社 | Circuit board resin composition, prepreg, laminate, resin sheet, multilayer printed wiring board, and semiconductor device |
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