CN101370879B - Curable resin composition, surface protection method, temporary fixation method, and separation method - Google Patents

Abstract

Disclosed is a curable resin composition for surface protection capable of forming a protection film, which is environmental friendly while having good adhesion strength and can be easily removed in a film form in water without leaving any adhesive residue, on a member to be processed. Also disclosed are a photocurable adhesive using such a curable resin composition, a method for temporarily fixing a member, and a method for separating a protection film. Specifically disclosed is a curable resin composition for surface protection, which is characterized by containing a polyfunctional (meth)acrylate (A), a monofunctional (meth)acrylate (B), and a resin (C) having a cyclopentadiene skeleton. Also specifically disclosed is a curable resin composition for surface protection, which is characterized by containing a polyfunctional (meth)acrylate (A), a monofunctional (meth)acrylate (B), a resin (C) having a cyclopentadiene skeleton, and a photopolymerization initiator (D). Further specifically disclosed is a curable resin composition for surface protection, which is characterized by containing a polyfunctional (meth)acrylate (A), a monofunctional (meth)acrylate (B), a resin (C) having a cyclopentadiene skeleton, a photopolymerization initiator (D), and a polar organic solvent (E).

Description

Curable resin composition, method for protecting surface, method of temporarily fixing and stripping means

Technical field

The present invention relates to various component is added destroy from cutting swarf etc. for the protection of processed component man-hour surface protection film, with ink etc., application is being carried out to processed component or lettering adds man-hour for the protection of not needing the temporary fixed surface protection film of application or lettering part (below also referred to as " protective membrane ".)。In addition, the method for protecting surface also relating to the curable resin composition being suitable for this surface protection film and use the surface of caking agent to processed component be made up of this curable resin composition to protect.

More specifically, the present invention relates to when peeling off tool member and cover the stripping means of the protective membrane on this component and be suitable for the Photocurable adhesive agent of this purposes.Also relate to the method for temporarily fixing of following processed component, that is, this processed component is adhered to base material, after processed component is processed, bonding portion is immersed in warm water, take off cured body, thus processed component is reclaimed.

Background technology

At metal sheet, mould, aluminium frame, plastic plate, semiconductor wafer, circuit substrate, pottery, optics or the sensor electronics such as glass or quartz, the processing of electric component, particularly cut, grinding, when the precision sizing such as grinding etc., in order to the machined surface by being coated to this processed component or circuit, sensor site etc. have the position of function, prevent to cut damage caused by water or produce scar because of cutting swarf etc., pollute, or it is damaged, use the surface protection film of temporarily guard block widely, pressure-sensitive adhesive thin slice is mainly used as this surface protection film.

In addition; in plating operation used in the circuit substrates such as printed-wiring board (PWB); for the part not needing plating on circuit, as the guard member preventing the pollution caused by plating liquid, material pressure-sensitive adhesive thin slice sanction being slit into arbitrary shape is also used to be used as sheltering part.

In addition, be not limited to electronics, electric component, for various Industrial products, the scale, decoration etc. of various label such as such as nameplate, mark etc., measuring instrument, also utilize various print process to carry out application or various lettering, when there being the part not needing application or lettering, being also attach pressure-sensitive adhesive thin slice in this part, carrying out thereafter application, lettering processing.

But; when pressure-sensitive adhesive thin slice is used as protective membrane during the processed component of processing; along with miniaturization, the miniaturization of parts now; exist and attach operation and become numerous and diverse, and sticking position slightly offset will as the shortcoming producing not good situation in the yield rate of product, designability.On parts in irregular situation, thin slice cannot follow that this is concavo-convex, and work in-process produces and peels off sometimes, thus processed component is polluted.In addition, use with the form fit of processed component cut out the material having cut pressure-sensitive adhesive thin slice, have and cut product and the shortcoming that needs the cost aspects such as expensive mould to make this sanction.

In order to solve these shortcomings, studied following method, namely, not laminating pressure-sensitive adhesive thin slice, but the ultra-violet solidified composition silk screen print method utilizing specific organic solvent, alkaline aqueous solution to remove is coated tool member face, and make its ultraviolet curing to carry out to be coated to, to shelter (with reference to patent documentation 1 ~ 3.)。

But owing to using alkaline aqueous solution, organic solvent, therefore clean operation is very numerous and diverse, and has problem in operating environment.In addition, when the surface of processed component have fine concavo-convex, organic solvent can not be made to soak into fully, protective membrane fully cannot be removed, thus produce the apparent problem of this processed component.

In addition, the slimming of semiconductor wafer, optics is (below also referred to as " grinding ".) be utilize following method to carry out, that is, all the time the circuit face surface protection thin slice of wafer, optics is protected, the so-called back side grinding method at the back side of grinding and circuit face opposite side.

Now, in general the thickness of the wafer on industrial level be 150 μm, but more and more require the wafer of slimming.When by slim for wafer turn to thinner thickness, grinding face (back side) becomes uneven phenomenon, i.e. circuit pattern back side transfer printing phenomenon because of the concavo-convex impact of circuit face will become obvious.

Can illustrate as shown below for the reason producing back side transfer printing phenomenon.The concavo-convex tracing ability of surface protection thin slice to the circuit of semiconductor wafer of pressure-sensitive adhesive now used is limited.Therefore, will press from both sides between bond layer and circuit face and be separated with gap (air bag), wafer is not directly supported by caking agent (protective layer) in this region.When utilizing grinding that wafer is become very thinization, will do not moved in the vertical direction between circuit die while compressed air pocket by the middle wafer of scribe line (street) supported, consequently, in this region not by grinding, thickening compared with other part.On the other hand, when there being the knur portions such as pad (bamp), wafer is by further grinding, consequently, thinning compared with other part.

Although this phenomenon can not become problem when the last processing thickness of wafer is more than 150 μm, but when by wafer grinding being (when being particularly finally processed as the thickness of less than 50 μm) when being less than 100 μm, or when the high projection on the wafer electric road surfaces such as pad is obviously very large (when being such as more than 100 μm), not only can reduce the bending strength of wafer widely, also can make wafer breakage in grinding in severe cases.

In addition, when by near wafer skiving to 50 μm, the edge crumbling of wafer, grinding water enter between wafer and sealer will become problem.Its reason is also be short of by the adhesion of surface protection thin slice and Waffer edge to cause.In addition, along with the slimming of wafer, for semiconductor wafer circuit face with pad with the projection of more than 100 μm being representative, attach typical semiconductor surface protection thin slice and the grinding of carrying out is inherently very difficult.

In general surface protection thin slice is in the past on polymer thin-film material, have the thin slice of bond layer as sealer.In order to follow the concavo-convex of circuit face, caking agent is designed to have low elastic modulus.But, if this tendency is excessively strong, then when thin slice is peeled off removing from wafer, very large stress can be applied to wafer, thus cause breakage.So, develop following energy-ray easy-stripping type protection thin slice, that is, before thin slice is peeled off, by irradiation ultraviolet radiation homenergic ray, caking agent is solidified, reduce the bonding force between wafer and protection thin slice.But during grinding, bond layer is uncured state and too soft, thus has wafer in grinding that damaged such problem occurs.

Patent documentation 4 discloses following wafer grinding method, that is, the wafer being formed with circuit attaches energy-ray easy-stripping type as above protection thin slice, with energy-ray by bond layer solidify after, carry out the back side grinding of wafer.But, due to caking agent and nonfluid, therefore abundant not to the concavo-convex tracing ability on wafer electric road surface.

On the other hand, the semiconductor surface protection thin slice of hot-melting type is disclosed in patent documentation 5.By being heated to 60 ~ 100 DEG C and melting the hot-melting type thin slice showing mobility can follow the concavo-convex of circuit face, show excellent grinding.But when temperature exceedes fusing point, this thin slice all can melting repeatedly.

In general, semiconductor wafer is by after thin slice fitted with protection, and at the film used in order to fixed chip and chip adhesive film, (Die Attachment Film is (later also referred to as " DAF ".) bonding process, utilize sputtering metallic membrane formation process during, heated sometimes.Consequently, the protection thin slice not good situation that melting is so is again produced sometimes.

In addition; also studied following method, that is, not coating surface protects thin slice; but by the ultraviolet hardening caking agent be dissolved in specific organic solvent being coated processing object plane make its ultraviolet curing to be coated to, protect it from the destruction such as cutting swarf adding man-hour.But due to an organic solvent, therefore clean operation is numerous and diverse, and has problem in operating environment.In addition, when fine concavo-convex, because organic solvent cannot soak into fully, protective membrane fully cannot be removed, therefore can produce the apparent problem of this processed component.

Patent documentation 1: JP 59-051962 publication

Patent documentation 2: Unexamined Patent 01-234477 publication

Patent documentation 3: Unexamined Patent 03-139573 publication

Patent documentation 4: Unexamined Patent 11-026406 publication

Patent documentation 5: JP 2000-038556 publication

Summary of the invention

With regard to the processing of the opticses such as metal sheet, mould, aluminium frame, plastic plate, semiconductor wafer, circuit substrate, pottery, glass or quartz or sensor electronics, electric component, particularly with regard to precision sizing such as cutting, grinding, grinding etc., expect to have following curing composition: for the protection of the machined surface of processed component or the functional part such as circuit and sensor site to avoid cutting water and enter or to produce scar or pollution because of cutting swarf etc.; Also expect to have following stripping means: after processing by be coated to protective membrane from machined object peel off when, do not have slurries remain, and Environmental, operability is also very excellent.

In addition, in order to improve the dimensional precision of the component after machining, expect to have the high and light-cured type caking agent that separability in water is excellent of hydrophobicity, bonding strength.Expect to have following light-cured type caking agent especially: when utilizing back side grinding method to carry out the slimming of semiconductor wafer, optics etc., the protection circuit face of wafer or the non-machined surface of optics, and there is above-mentioned characteristic.

In addition, as to above-mentioned illustrative optics, sensor electronics, electric components etc. are protected these components when processing and are avoided cutting the protective membrane that water enters the caused damage such as component surface or cutting swarf or pollution, and as preventing the protective membrane of the pollution caused by plating liquid used in the circuit substrates such as printed-wiring board (PWB), in addition, as to being not limited to electronics, the various Industrial products of electric component, such as nameplate, the various labels such as mark, the scale of measuring instrument, ornaments etc. carry out application, lettering adds the temporary protective film being suitable for man-hour carrying out sheltering, expect to have the curable resin composition of the good surface protection of workability.

The present inventor is studied to address these problems, and obtains following opinion, completes the present invention.

A () following stripping means can reach above-mentioned purpose; namely; processed component arranges protective membrane; after processed component is processed; the surface of processed component and/or protective membrane attaches thin slice; be separated into processed component and protective membrane and thin slice, or be separated into protective membrane and processed component and thin slice.The material of described protective membrane is the concavo-convex material with enough tracing abilities to metal sheet, semiconductor wafer, optics, and has enough rigidity as the protective membrane adding man-hour, and bonding strength is high and formed by good curable resin composition.

B () following curable resin composition can reach above-mentioned purpose, namely, it is the concavo-convex material with enough tracing abilities of the circuit face to wafer, optics, and be the composition with enough rigidity as supporter during grinding, using (methyl) Acrylic Acid Monomer and there is the resin of cyclopentadienyl skeleton as composition.

C () curable resin composition containing specific (methyl) Acrylic Acid Monomer is suitable for use as the surface protection film when the processed component of processing; in addition; if have the material of specific viscosity; then silk screen print method can be applied; in addition; the method for protecting surface of following processed component can also be provided; namely; when using the protective membrane formed by this curable resin composition; what can prevent processed component adds the damage in man-hour or the generation of dirt, and does not have the stripping of surface protection film to remain.

The present invention has following main idea.

(1) a kind of curable resin composition of surface protection; it is characterized in that, containing (A): multifunctional (methyl) acrylate, (B): simple function (methyl) acrylate, (C): the resin with cyclopentadienyl skeleton.

(2) a kind of curable resin composition of surface protection; it is characterized in that, containing (A): multifunctional (methyl) acrylate, (B): simple function (methyl) acrylate, (C): there is the resin of cyclopentadienyl skeleton, (D): Photoepolymerizationinitiater initiater.

(3) a kind of curable resin composition of surface protection; it is characterized in that, containing (A): multifunctional (methyl) acrylate, (B): simple function (methyl) acrylate, (C): there is the resin of cyclopentadienyl skeleton, (D): Photoepolymerizationinitiater initiater, (E): polar organic solvent.

(4) curable resin composition of the surface protection according to any one of above-mentioned (1) to (3), wherein, (C) has ester group or hydroxyl in molecule.

(5) a kind of curable resin composition of surface protection, it is characterized in that, containing (F): on the end or side chain of molecule, there is more than one (methyl) acryl and molecular weight (methyl) acrylate more than 500; (G): (methyl) acrylate beyond (F); (D): Photoepolymerizationinitiater initiater.

(6) curable resin composition of the surface protection according to above-mentioned (5), wherein, (F) is selected from polyhutadiene; Polyisoprene; And more than one in the hydrogenation thing of polyhutadiene or polyisoprene.

(7) curable resin composition of the surface protection according to above-mentioned (5) or (6), wherein, also containing (H): inorganic filling material.

(8) curable resin composition of the surface protection according to above-mentioned (7), wherein, (H) is silicon-dioxide.

(9) curable resin composition of the surface protection according to any one of above-mentioned (1) to (8); wherein, (A), (B), (F) and (G) have hydrophobic (methyl) acrylate.

(10) curable resin composition of the surface protection according to above-mentioned (1), wherein, (A) containing 1 ~ 50 mass parts, (B) of 5 ~ 95 mass parts, 0.1 ~ 50 mass parts (C).

(11) curable resin composition of the surface protection according to above-mentioned (2); wherein, (A) containing 1 ~ 50 mass parts, (B) of 5 ~ 95 mass parts, (C) of 0.1 ~ 50 mass parts, (D) of 0.1 ~ 20 mass parts.

(12) curable resin composition of the surface protection according to above-mentioned (3); wherein, (C), (D) of 0.1 ~ 20 mass parts, (E) of 0.5 ~ 10 mass parts of (A) containing 1 ~ 50 mass parts, (B) of 5 ~ 95 mass parts, 0.1 ~ 50 mass parts.

(13) curable resin composition of the surface protection according to above-mentioned (5), wherein, (F) containing 20 ~ 90 mass parts, (G) of 10 ~ 80 mass parts, 0.1 ~ 20 mass parts (D).

(14) curable resin composition of the surface protection according to any one of above-mentioned (5) to (9) and (13), wherein, viscosity is at more than 5000mPas.

(15) a kind of caking agent; it is characterized in that, the curable resin composition of the surface protection according to any one of above-mentioned (1) to (4), (9), (10), (11), (12) and (13) is formed.

(16) a processed component, is characterized in that, the cured body that the curable resin composition arranging the surface protection according to any one of above-mentioned (1) to (14) is from the teeth outwards formed forms.

(17) a kind of method for protecting surface of processed component; it is characterized in that; on the surface of processed component; the protective membrane solidified by the curable resin composition of the surface protection according to any one of above-mentioned (1) to (14) is set; after processed component is processed, said protection film is peeled off from processed component.

(18) method for protecting surface of the processed component according to above-mentioned (17), wherein, when being peeled off from processed component by protective membrane, is immersed in major general's protective membrane in the warm water of less than 90 DEG C.

(19) method for protecting surface of the processed component according to above-mentioned (17) or (18), wherein, utilizes silk screen print method to arrange protective membrane on the surface of processed component.

(20) a kind of method of temporarily fixing of processed component; it is characterized in that; using the curable resin composition of the surface protection according to any one of above-mentioned (1) to (14) by processed component and substrate bonding; and after making it solidify; impregnated in the warm water of less than 90 DEG C after this processed component is processed, take off the cured body of the curable resin composition of above-mentioned surface protection.

(21) a kind of stripping means of protective membrane; the protective membrane that the curable resin composition that the surface of processed component arranges the surface protection according to any one of above-mentioned (1) to (14) is formed; after processed component is processed; said protection film is peeled off from processed component; it is characterized in that; the surface of processed component and/or protective membrane attaches thin slice; be separated into processed component and protective membrane and thin slice, or be separated into protective membrane and processed component and thin slice.

(22) stripping means of the protective membrane according to above-mentioned (21), wherein, when being separated into processed component and protective membrane and thin slice, at least makes protective membrane contact with warm water.

(23) stripping means of the protective membrane according to above-mentioned (21) or (22), wherein, the thin slice be attached on the surface of processed component and/or protective membrane is the pressure-sensitive adhesive thin slice being formed with adhesive linkage on base material.

(24) stripping means of the protective membrane according to above-mentioned (23), wherein, the adhesive linkage of thin slice is energy ray-curable caking agent.

(25) stripping means of the protective membrane according to above-mentioned (23) or (24), wherein, to thin slice irradiation energy ray, protective membrane is integrated with thin slice adhesive linkage.

The stripping means of protective membrane of the present invention; because the protective membrane formed by curable resin composition has light solidified because it forms; namely visible ray or ultraviolet isoreactivity energy-ray is utilized to solidify; therefore, compared with the method for use hot-melt adhesive in the past, Labor-saving, energy-saving, operation shortening can be realized.

In addition; should the protective membrane that be formed by curable resin composition due to high-adhesive-strength can not be embodied with affecting by adding man-hour cutting water etc. used; therefore not easily offsetting is produced in the man-hour that adds of component; protection can be provided to component, enter to avoid cutting water or produce damage because of cutting swarf etc. or pollute.In addition, when peeling off protective membrane from the processed component after processing, by attaching thin slice on the surface of processed component and/or protective membrane, will be easy to, do not have slurries to remain, workability is excellent.

In addition; when using the protective membrane of specific composition; there is following advantage: reduce bonding strength by the warm water, the particularly warm water of less than 90 DEG C that this protective membrane are contacted more than 30 DEG C, reduce between component or the engaging force of component and fixture, therefore can be easy to recovery component.So, compared with the caking agent in the past used as surface protection film, do not need to use expensive, inflammableness strong or can produce the organic solvent of harmful gas.

In addition, because thin slice used is the pressure-sensitive adhesive thin slice being formed with adhesive linkage on base material, therefore workability is excellent.Particularly when the adhesive linkage of thin slice is energy ray-curable caking agent, by irradiation energy ray, bonding force reduces, and then the protective membrane being coated on processed component becomes to be integrated with thin slice and peels off, and therefore the recovery of component is not numerous and diverse.

In addition, for the curable resin composition of specific preferably compositing range, cured body contacts with the warm water of less than 90 DEG C and swelling, and can reclaim from component with film like, therefore workability is excellent.

The curable resin composition of surface protection of the present invention has the viscosity can applying silk screen print method in a preferred embodiment, therefore can realize Labor-saving, energy-saving, operation shortening.

Embodiment

The curable resin composition of protective membrane is formed, containing (A): multifunctional (methyl) acrylate, (B): simple function (methyl) acrylate, (C): there is the resin of cyclopentadienyl skeleton, (D): Photoepolymerizationinitiater initiater in the present invention.

As (A) used in above-mentioned curable resin composition, be in oligopolymer/polymer end or side chain more than 2 by (methyl) acrylated multifunctional (methyl) origoester acrylate/polymer or the monomer with more than 2 (methyl) acryls.

As their example, as multifunctional (methyl) origoester acrylate/polymer, can 1 be enumerated, 2-polybutadiene ends urethane (methyl) acrylate (" TE-2000 " of such as Japanese Cao Da Inc., " TEA-1000 "), the hydrogenation thing (" TEAI-1000 " of such as Japanese Cao Da Inc.) of aforesaid propylene acid esters, 1, 4-polybutadiene ends urethane (methyl) acrylate (" BAC-45 " of such as Osaka organic chemistry Inc.), polyisoprene end (methyl) acrylate, Polyester urethane (methyl) acrylate, polyethers system urethane (methyl) acrylate, polyester (methyl) acrylate, two A type epoxy (methyl) acrylate (" Biscoat#540 " of such as Osaka organic chemistry Inc., " the Biscoat VR-77 " of Showa polymer Inc.) etc.

In addition, in the middle of the monomer with more than 2 (methyl) acryls, as 2 officials' energy (methyl) acrylate monomers, two (methyl) vinylformic acid 1,3 butylene glycol ester can be enumerated, two (methyl) vinylformic acid BDO ester, two (methyl) vinylformic acid 1,6-hexylene glycol ester, two (methyl) vinylformic acid 1,9-nonanediol ester, two (methyl) vinylformic acid DOPCP, tetrahydro-dicyclopentadiene base (dicyclopentanyl) two (methyl) acrylate, 2-ethyl-2-butyl-propylene glycol (methyl) acrylate, neopentyl glycol modification TriMethylolPropane(TMP) two (methyl) acrylate, stearic acid modified pentaerythritol diacrylate, polypropylene glycol two (methyl) acrylate, two (4-(methyl) the acryloxy diethoxy phenyl) propane of 2,2-, two (4-(methyl) acryloxy propoxyphenyl) propane of 2,2-, two (4-(methyl) acryloxy tetraethoxy phenyl) propane of 2,2-etc.

As 3 officials' energy (methyl) acrylate monomers, trimethylolpropane tris (methyl) acrylate, three [(methyl) acryloyl-oxyethyl] isocyanuric acid ester etc. can be enumerated.

Can above (methyl) acrylate monomer as 4 officials, dihydroxy methylpropane four (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane oxyethyl group four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate etc. can be enumerated.

(A) used in above-mentioned curable resin composition more preferably hydrophobic material.In water miscible situation; due to add the protective membrane that formed by curable resin composition man-hour swelling because cutting water, causing position offset or peel off, cutting water and enter or be cut bits equivalent damage or pollution; working accuracy is likely deteriorated, therefore not ideal enough.Even wetting ability, if the protective membrane formed by this curable resin composition can not because of water swelling or local dissolution greatly, then also can use.

The addition of (A) used in above-mentioned curable resin composition, in total amount 100 mass parts of (A) and (B), is preferably 1 ~ 50 mass parts, is more preferably 5 ~ 40 mass parts.If more than 1 mass parts, then do not have that separability reduces, a situation of the protective membrane that formed by curable resin composition not film-like, if below 50 mass parts, then do not have cure shrinkage and become excessive and make the situation that the cementability at initial stage reduces.

As (B) used in above-mentioned curable resin composition, can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) isodecyl acrylate, (methyl) dodecylacrylate, (methyl) octadecyl acrylate, (methyl) phenyl acrylate, (methyl) cyclohexyl acrylate, tetrahydro-dicyclopentadiene base (methyl) acrylate, dicyclopentenyl (methyl) acrylate, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) isobornyl acrylate, methoxylation ring triolefin in the last of the ten Heavenly stems (methyl) acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxybutyl, tetrahydrofurfuryl (methyl) acrylate, 2-hydroxyl-3-phenoxy propyl (methyl) acrylate, (methyl) glycidyl acrylate, caprolactone modification tetrahydrofurfuryl (methyl) acrylate, 3-chlorine-2-hydroxyl propyl group (methyl) acrylate, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, t-butylamino ethyl (methyl) acrylate, ethoxy carbonyl methyl (methyl) acrylate, phenolethylene oxide modification acrylate, phenol (oxyethane 2 mole) acrylate, phenol (oxyethane 4 mole) acrylate, the ethylene-oxide-modified acrylate of p-cumylphenol, Nonylphenol ethylene oxide modification acrylate, nonylphenol (oxyethane 4 mole) acrylate, nonylphenol (oxyethane 8 mole) acrylate, nonylphenol (propylene oxide 2.5 mole) acrylate, 2-ethylhexyl Trivalin SF acrylate, ethylene-oxide-modified phthalandione (methyl) acrylate, ethylene-oxide-modified succsinic acid (methyl) acrylate, trifluoroethyl (methyl) acrylate, vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, ω-carboxyl-polycaprolactone list (methyl) acrylate, phthalandione monohydroxy ethyl (methyl) acrylate, (methyl) acrylic acid dimer, β-(methyl) acryloyl-oxyethyl hydrogenated diene succinate, n-(methyl) acryloxyalkyl hexahydro-phthalic imidine etc.

(B) used in above-mentioned curable resin composition same with (A) more preferably hydrophobic material.In water miscible situation; due to add the protective membrane that formed by curable resin composition man-hour swelling because cutting water, causing position offset or peel off, cutting water and enter or be cut bits equivalent damage or pollution; working accuracy is likely deteriorated, therefore not ideal enough.Even wetting ability, if the protective membrane formed by this curable resin composition can not because of water swelling or local dissolution greatly, then also can use.

The addition of (B) used in above-mentioned curable resin composition, in total amount 100 mass parts of (A) and (B), is preferably 5 ~ 95 mass parts, is more preferably 10 ~ 80 mass parts.If more than 5 mass parts, then can obtain the cementability at initial stage fully, if below 95 mass parts, then can obtain sufficient separability, can obtain with film like the protective membrane formed by curable resin composition.

In addition; in the cooperation composition of above-mentioned (A) and (B); by also having the phosphoric acid ester of vinyl or (methyl) acryl by (methyl) acryloyl-oxyethyl phosphate ester acid, dibutyl 2-(methyl) acryloyl-oxyethyl phosphate ester acid, dioctyl 2-(methyl) acryloyl-oxyethyl phosphoric acid ester, phenylbenzene 2-(methyl) acryloyl-oxyethyl phosphoric acid ester, (methyl) acryloyl-oxyethyl polyoxyethylene glycol acid phosphoric acid ester etc., the adhesion with metal covering can be improved further.

In addition; in the present invention; (methyl) acrylate is divided into (F): in the end or side chain of molecule, there is more than one (methyl) acryl and molecular weight (methyl) acrylate more than 500 and (G): (methyl) acrylate beyond (F), also preferably uses containing (F), (G) and (D): the curable resin composition of the surface protection of Photoepolymerizationinitiater initiater.

Here, as (F), multifunctional (methyl) origoester acrylate/polymer of commercially available product illustrated in above-mentioned (A) can be enumerated.

And, for the molecular weight of (F), based on guaranteeing the reason of the viscosity realizing silk screen print method, select more than 500.Although for the necessity that its upper limit does not limit technically; but as the curable resin composition of surface protection; from the viewpoint of operability; preferably aqueous; in addition; based on the deliquescent reason in other (methyl) acrylate monomers, preferably below 100000.As the molecular weight of (F), more preferably 1000 ~ 50000.

For (F), be preferably selected from polyhutadiene; Polyisoprene; And more than one in the above two hydrogenation thing, this is because, when the cured body of the curable resin composition by surface protection impregnated in warm water, character that this cured body peels off from bur can be strengthened (hereinafter referred to as " separability ".)。

In the present invention, the addition of (F), in (F) total amount 100 mass parts with (G), is preferably 20 ~ 90 mass parts, is more preferably 25 ~ 85 mass parts.If more than 20 mass parts, then separability is very abundant, can guarantee to apply the viscosity of silk screen printing.In addition, if below 90 mass parts, then can not produce viscosity and rise and operability is reduced.

(F) preferred hydrophobic material.In water miscible situation, due to the swelling or local dissolution of the cured body of the curable resin composition of surface protection when machining, thus cause position to offset, working accuracy is likely deteriorated, therefore not ideal enough.But, even wetting ability, as long as the cured body of the curable resin composition of this surface protection can not because of water swelling or local dissolution greatly, then also can use.

In addition, as (G), multifunctional (methyl) acrylate monomer ((methyl) acrylate monomer of 2 officials' energy, 3 officials' energy and 4 officials energy) illustrated in simple function (methyl) acrylate monomer illustrated in above-mentioned (B), above-mentioned (A) can be enumerated.

The addition of (G) used in the present invention, in total amount 100 mass parts of (F) and (G), is preferably 10 ~ 80 mass parts, is more preferably 15 ~ 75 mass parts.If be less than 10 mass parts, then the cementability at initial stage likely reduces, if more than 80 mass parts, then separability likely reduces.

In addition; in the cooperation composition of above-mentioned (F) and (G); by also having the phosphoric acid ester of vinyl or (methyl) acryl by (methyl) acryloyl-oxyethyl phosphate ester acid, dibutyl 2-(methyl) acryloyl-oxyethyl phosphate ester acid, dioctyl 2-(methyl) acryloyl-oxyethyl phosphoric acid ester, phenylbenzene 2-(methyl) acryloyl-oxyethyl phosphoric acid ester, (methyl) acryloyl-oxyethyl polyoxyethylene glycol acid phosphoric acid ester etc., the adhesion with metal covering can be improved further.

(G) used in the present invention same with (F) more preferably hydrophobic material.In water miscible situation; due to swelling because cutting water at the protective membrane formed by curable resin composition adding surface protection in man-hour, causing position offset or peel off, cutting water and entering or be cut bits equivalent damage or pollution; working accuracy is likely deteriorated, therefore not ideal enough.But, even wetting ability, as long as the protective membrane formed by curable resin composition of this surface protection can not because of water swelling or local dissolution greatly, then also can use.

In the curable resin composition of surface protection of the present invention, by going back and using (C): the resin with cyclopentadienyl skeleton, surface cure can be improved.

As (C), the petroleum resin manufactured for main raw material with the cyclopentadiene extracted from C 5 fraction can be enumerated.Specifically, " Quintone 1700 ", " Quintone 1500 ", " Quintone 1325 " etc. of Nippon Zeon can be enumerated.

As (C) used in curable resin composition, as long as have the resin of cyclopentadienyl skeleton, no matter be then which kind of material can, but preferably softening temperature is the material of 50 DEG C to 200 DEG C, in addition, from the viewpoint of deliquescent, preferred number average molecular weight (Mn) is the material of 300 to 600.

(C) used in curable resin composition, relative to total amount 100 mass parts of (A) and (B), is preferably 0.5 ~ 50 mass parts, is more preferably 1 ~ 40 mass parts.More than 0.5 mass parts, will film be formed and do not have slurries remain, below 50 mass parts, then can obtain enough cementabilities.

As (D) used in curable resin composition, being the material in order to utilize visible rays or ultraviolet isoreactivity energy-ray to make curable resin composition sensitization coordinate to promote the photocuring of curable resin composition, known various Photoepolymerizationinitiater initiater can be used.

Specifically, benzophenone or derivatives thereof can be enumerated; Dibenzoyl or derivatives thereof; Anthraquinone or derivatives thereof; The benzoin derivatives such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, bitter almond oil camphor propyl ether, benzoin isobutyl ether, benzil dimethyl ketal; The acetophenone derivs such as diethoxy acetophenone, 4-tertiary butyl Trichloroacetophenon; 2-dimethyl aminoethyl benzoic ether, p-dimethyl aminoethyl benzoic ether; Diphenyl disulfide, thioxanthone or derivatives thereof; Camphorquinone, 7,7-dimethyl-2,3-dioxa dicyclo [2.2.1] heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxa dicyclo [2.2.1] heptane-1-carboxyl-2-bromo-ethyl ester, 7,7-dimethyl-2,3-dioxa dicyclo [2.2.1] heptane-1-carboxyl-2-methyl ester, 7, the camphorquinone derivative such as 7-dimethyl-2,3-dioxa dicyclo [2.2.1] heptane-1-carboxylic acid chloride; The alpha-aminoalkyl benzophenone derivatives such as 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butanone-1; Benzoyl diphenyl phosphine oxide, 2; 4; 6-trimethyl benzoyl diphenyl base phosphine oxide, benzoyl diethoxy phosphine oxide, 2; 4; 6-trimethylbenzoyl Dimethoxyphenyl phosphine oxide, 2; the acylphosphine oxide derivatives etc. such as 4,6-trimethylbenzoyl diethoxy phenyl phosphine oxide.Photoepolymerizationinitiater initiater can use one, or combinationally uses two or more.

The addition of (D) used in curable resin composition is relative to total 100 mass parts of (A) and (B) or (F) and (G), be preferably 0.1 ~ 20 mass parts, be more preferably 3 ~ 20 mass parts.If more than 0.1 mass parts, then can obtain the effect promoting solidification, if below 20 mass parts, then can obtain enough curing speeds.As more preferred mode, by adding (D) of more than 3 mass parts, do not solidify with just can relying on rayed amount, the degree of crosslinking of the cured body of curable resin composition uprises in addition, position offsetting etc. can not be caused when machining, or separability improves, more preferred from the viewpoint of these.

In addition; by (E) polar organic solvent is used together with (A), (B), (C) and (D) or the curable resin composition such as (F), (G) and (D); just can reliably realize following phenomenon; namely; the protective membrane formed by curable resin composition contacts with warm water and swelling easily, and bonding strength is reduced.

About (E), its boiling point preferably more than 50 DEG C less than 130 DEG C.When selecting the polar organic solvent of boiling point in above-mentioned scope, more reliably can realize the curable resin composition after solidifying and contact with warm water and make the phenomenon that bonding strength reduces, therefore preferably.

In addition, as this kind of polar organic solvent, such as, can enumerate alcohol, ketone, ester etc., and according to the result of study of the present inventor, wherein preferred alcohols.

As alcohol, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol, primary isoamyl alcohol, 2-ethyl-butyl alcohol etc. can be enumerated.

Wherein, the methyl alcohol of preferred boiling point below 120 DEG C, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, more preferably methyl alcohol, ethanol, Virahol, propyl carbinol.Particularly preferably boiling point below 100 DEG C, there is no what foul smell, the ethanol not being designated as medicinal violent in toxicity, Virahol.

(E) addition is relative to total amount 100 mass parts of (A) in curable resin composition and (B) or (F) and (G), be preferably 0.5 ~ 30 mass parts, be more preferably 1 ~ 20 mass parts.If more than 0.5 mass parts, then can guarantee separability, if below 30 mass parts, then do not worry that the cementability at initial stage reduces, the cured body of curable resin composition can be peeled off with film like.

Curable resin composition of the present invention, in order to improve its package stability, can use a small amount of polymerization retarder.As polymerization retarder, such as can enumerate toluhydroquinone, quinhydrones, 2,2-methylene radical-bis-(4-methyl-6-tert-butylphenol), catechol, hydroquinone monomethyl ether, single tertiary butylated hydroquinone, 2,5-di-tert-butyl hydroquinone, para benzoquinone, 2,5-phenylbenzene-para benzoquinone, 2,5-di-t-butyl-para benzoquinone, picric acid, citric acid, thiodiphenylamine, tert-butyl catechol, 2-butyl-4-hydroxyanisol and 2,6 ditertiary butyl p cresol etc.

The usage quantity of these polymerization retarders is relative to total amount 100 mass parts of (A) in curable resin composition and (B) or (F) and (G), be preferably 0.001 ~ 3 mass parts, be more preferably 0.01 ~ 2 mass parts.If more than 0.001 mass parts, then do not have the situation that package stability reduces, if below 3 mass parts, then neither have the situation that cementability reduces, do not have uncured situation yet.

Curable resin composition of the present invention, according to its usage, particularly in the situations such as silk screen printing, except above-mentioned each composition, can also add the inorganic filling material of (H).

As (H), spherical alumina, pulverizing aluminum oxide, magnesium oxide, beryllium oxide, titanium oxide etc. can be enumerated oxide-based; Boron nitride, silicon nitride, aluminum nitride and other nitride class; The carbon compounds such as silicon carbide; The hydrated metal such as aluminium hydroxide, magnesium hydroxide class; The filler metal such as copper, silver, iron, aluminium, nickel; The metal alloy packing materials such as titanium; The carbon such as diamond, carbon system packing material; The silicon-dioxide such as quartz, silica glass, fused silica, spherical silicon dioxide, pyrogenic silica, silica sand, wollastonite, clay, talcum, calcium carbonate, granulated glass sphere, white sand microballoon (silasuballoon) etc.These inorganic filling materials can use a kind of or two or more.In these inorganic filling materials, as the material easily obtained, and consider the light solidified of the curable resin composition of surface protection, preferred silicon-dioxide, considers screen printability, then more preferably drying process silicon-dioxide.

So-called drying process silicon-dioxide is in the middle of the silicon dioxide powders such as crystalline silica silica flour, fused silica powder, spherical silicon dioxide powder and pyrogenic silica, the white carbon black that is commonly called as, such as under the existence of hydrogen and oxygen, by silicon tetrachloride thermolysis and the silicon-dioxide manufactured under the high heat of about 1000 DEG C.This drying process silicon-dioxide, due to silica interior Stability Analysis of Structures, therefore can expose silanol group at particle surface.

In addition, in the present invention, also can be in the middle of drying process silicon-dioxide, in order to carry out surface modification and dispersed improvement, and be reacted by the silanol group that makes to be present in silica sphere and organic silicon halide compound or alcohols and carry out hydrophobization and the surface treated silicon-dioxide that obtains.As this kind of dry type silicon-dioxide, such as, can enumerate " Aerosil 130 ", " Aerosil 200 ", " Aerosil 300 ", " Aerosil 380 ", " Aerosil R972 " (being all Japanese Aerosil Inc.), " Cab-O-Sil " (G.L.Cabot Corp. system), " DC Fine Silica " (Dow Corning Inc.), " Fransil 251 " (Farnsol Inc.) etc.

Above-mentioned dry type silicon-dioxide is when coating composition or caking agent etc., use widely there is not the object of vertical liquid for the structural viscosity improving liquid self, by adding dry type silicon-dioxide, the viscosity can carrying out silk screen print method can be adjusted to easily.

As the viscosity of the curable resin composition of surface protection of the present invention, preferably at more than 5000mPas.If at more than 5000mPas, then do not have vertical liquid, good protective membrane can be obtained.More preferably at more than 10000mPas, more good protective membrane can be obtained in silk screen print method.In addition, for the upper limit of viscosity, suitably can select according to the usage of this curable resin composition, when silk screen printing, preferably at below 2000000mPas, in the situations such as brushing, preferably at below 100000mPas.

In addition; the curable resin composition of surface protection of the present invention, in the scope not damaging object of the present invention, also can use usually the additives such as various elastomerics, solvent, extender, strengthening agent, softening agent, thickening material, dyestuff, pigment, fire retardant, silane coupling agent and tensio-active agent such as acrylic rubber used, urethanes, acrylonitrile-butadiene-styrene (ABS) rubber.

So-called thin slice used in the present invention is at kraft paper, Japan paper, the stationeries such as crepe paper, artificial silk, cotton, glass, polyester, vinylon etc. singly spin or the weaving cotton cloth of blending etc., split-film fibre (split fiber) cloth of polypropylene etc., artificial silk, polypropylene, aromatic polyamide, polyester, the dry goods such as the Non-woven fabrics of glass etc., cellulose film, acetic ester, polyvinyl chloride, polyethylene, the polyolefine such as polypropylene, polyester, tetrafluoroethylene, polyethylene terephthalate (PET), the plastics film class of polyimide etc., natural rubber, styrene butadiene ribber, isoprene-isobutylene rubber, the rubber sheet class of the independent or mixture of (co) polychloroprene rubber etc., urethane, polyethylene, isoprene-isobutylene rubber, polystyrene, (co) polychloroprene rubber, the foam class of acrylic rubber etc., aluminium, copper, on the base materials such as the tinsel class of stainless steel etc., by coating, infiltration etc. is formed with natural rubber, styrene butadiene rubbers, isobutene rubber, synthetic polyisoprene, styrene isoprene rubber segmented copolymer, the rubber series such as styrene-butylene block multipolymer, acrylic acid series, silicone-based, polyurethane series, the material of the adhesive linkage of polyvinyl ether system caking agent etc.Label film adhesive tape, adhesive film, adhesive sheet or the jointing tape etc. such as so-called label (label), gummed label (sticker) can be used.

In addition, as long as be coated with on above-mentioned supporter epoxy, polyimide system, polyurethane series resin Thermocurable adhesive sheet etc. can be attached to the lamellar material of processed component surface, then do not limit its shape, form.

In the middle of thin slice used in the present invention, from the viewpoint of the simplicity attaching operation, preferably there is on above-mentioned base material the pressure-sensitive adhesive thin slice of the pressure-sensitive adhesive layer of acrylic copolymer etc.

In addition, if the bond layer of above-mentioned thin slice uses energy ray-curable caking agent, then after irradiation energy ray, bonding force obviously reduces, and therefore can peel off from processed component easily, be desirable in this.Specifically, as the thin slice employing energy ray-curable caking agent, dicing tape (dicing tape), back side grinding adhesive tape (backgrind tape) etc. that fixing caking agent when can to enumerate as base material be the grinding/cutting of comparing the polyvinyl chloride with retractility, the circuit substrate employing polyolefinic silicon wafer, glass reinforced epoxy resin, pottery etc. etc. uses.

They are after processing, by irradiation energy ray, and base material is extended, jack-up, take off the processed components such as objective chip and the thin slice that is separated.Such as can enumerate following method etc., that is, dicing tape, after coating film protection, be attached to behind the surface of the processed component being coated with protective membrane as fixing caking agent by processed component, utilize the cutting units such as scribing machine to carry out cutting processing.Then, irradiation energy ray and weaken bonding force, extends this adhesive tape, takes off processed component.

Energy ray-curable caking agent with the pressure adhesive be made up of acrylic copolymer and utilize energy-ray to be polymerized compound for principal constituent; therefore integrally peel off with the above-mentioned protective membrane formed by curable resin composition; due to this point, also can similarly obtain effect not numerous and diverse in the recovery of component.

And according to processing form, thin slice both can be attached on protective membrane before processing in advance, also can attach on protective membrane after processing.

In the present invention; after processed component and/or protective membrane have attached above-mentioned thin slice; by applying suitable external force to processed component, protective membrane, thin slice etc., just can be separated into processed component and protective membrane and thin slice, or be separated into protective membrane and processed component and thin slice.

The present invention is a kind of stripping means of protective membrane; it is characterized in that; the protective membrane formed by curable resin composition is set on the surface of processed component; after the processed component of processing; said protection film is peeled off from processed component, wherein, the surface of processed component and/or protective membrane attaches thin slice; be separated into processed component and protective membrane and thin slice, or be separated into protective membrane and processed component and thin slice.

According to a preferred embodiment of the invention, when by processed component and protective membrane and slice separates, by least making protective membrane contact warm water, protective membrane will be swelling, and softening.Thus, protective membrane has attached thin slice, protective membrane is easy to integrally peel off with thin slice, can reclaim processed component easily, therefore can obtain the excellent effect of operability.

In addition, the present invention is the method for temporarily fixing of processed component as follows.

That is, be the method for temporarily fixing of following component, first, use the curable resin composition contacting bonding strength with the warm water of less than 90 DEG C and can reduce, processed component is adhered to base material, by curable resin composition solidification, carries out temporary fixed.Then, after the component this be temporarily fixed is processed, if needed, the component that this is processed impregnated in warm water together with base material, takes off the caking agent that have cured.Thus, just can not with an organic solvent the various component such as processing optical component accurately.

According to a preferred embodiment of the invention, when component is taken off, by the cured body of curable resin composition to be contacted with the warm water of less than 90 DEG C and swelling, make it to reclaim from component with film like, thus the excellent effect of operability can be obtained.

In method of temporarily fixing of the present invention, the caking agent be made up of curable resin composition of the present invention is used can reliably to obtain above-mentioned effect, therefore preferably.

The present invention, by using the moderately warm water of warmed-up less than 90 DEG C, can realize separability at short notice, from the viewpoint of productive be desirable.The temperature of warm water is 30 DEG C ~ 90 DEG C, is preferably 40 ~ 80 DEG C.

If use warm water, then the protective membrane formed by curable resin composition can be slightly swelling or softening at short notice, is therefore being attached to after on protective membrane by thin slice, can take off while integrated with thin slice for the protective membrane of film like, so preferably.

And for the method that protective membrane contacts with warm water, being not particularly limited, can be the method that impregnated in the processed member integrated being provided with protective membrane in warm water or attach after only flooding protective membrane part thin slice.Can also be the method for material soaking in warm water by having attached thin slice on the processed component being provided with protective membrane.By impregnated in after in warm water, thin slice being peeled off, just more easily can be separated into processed component and protective membrane and thin slice, or be separated into protective membrane and processed component and thin slice.

In the present invention; use by containing (A) multifunctional (methyl) acrylate, (B) simple function (methyl) acrylate, (C) has the resin of cyclopentadienyl skeleton, the curable resin composition of (D) Photoepolymerizationinitiater initiater is formed protective membrane; reliably can obtain the effect of foregoing invention, therefore preferably.Use the protective membrane formed by the curable resin composition also containing (E) polar organic solvent, then more preferred.

By the protective membrane formed by curable resin composition of the present invention is contacted with warm water; because the residual deforming stress produced when solidification is removed; therefore bonding strength reduces; and especially the vapour pressure of (E) polar organic solvent and peeling force one work, and can be taken off from processed component with film like by protective membrane easily.

In the present invention, the material can carrying out temporary fixed component and base material is not particularly limited, when using ultraviolet hardening caking agent, preferably by the component that can form through ultraviolet material or base material.As this kind of material, such as, can enumerate crystal component, glass component, plastic member, wafer.

Method of temporarily fixing of the present invention go for glass lens, plastic lens, wafer and CD processing in temporary fixed.

With regard to the using method of the caking agent in method of temporarily fixing, if imagination uses Photocurable adhesive agent as the situation of caking agent, then such as can list following method etc., namely, coating adhesive in appropriate amount on the component that will fix or a side of base material or the face of two sides, through this component or base material, visible ray or ultraviolet are irradiated to above-mentioned caking agent, Photocurable adhesive agent is solidified and temporary fixed.

Thereafter, the component be temporarily fixed is cut into required shape, after implementing the processing such as grinding, grinding, perforate, by this component is immersed in water, is preferably immersed in warm water, just the cured article of caking agent can be peeled off from component.

In addition; the present invention is a kind of method for protecting surface of processed component; it is characterized in that; use above-mentioned curable resin composition be coated to processed component surface and after making it solidify; process this processed component; thereafter impregnated in the warm water of less than 90 DEG C, the cured body of curable resin composition is taken off.That is, by being coated with above-mentioned curable resin composition at the green surface of processed component and making it solidify, just can prevent from adding the situation polluted this surface man-hour, produce chip.

The method for protecting surface of processed component of the present invention is the method for protecting surface of following processed component; it is characterized in that; the protective membrane formed by the curable resin composition of surface protection is set on the surface of processed component; after processed component is processed, said protection film is peeled off from processed component.

The damage of the processed component that so just can avoid adding that the cutting water occurred man-hour enters, cutting swarf etc. is caused or pollution, thus optics, sensor electronics, the electric components etc. such as protection pottery, glass, quartz.In addition; the pollution caused by plating liquid used in the circuit substrates such as printed-wiring board (PWB) can be prevented, add man-hour for carrying out the suitable protective membrane sheltered and playing a role as the application such as scale, decoration of the various label such as nameplate, mark, measuring instrument, lettering.

The method of protective membrane is set as the surface at processed component, brushing, various cladding process, silk screen print method, pad printing method (tampo print), the arbitrary coating process such as spraying method, casting, pickling process can be used.Wherein, more preferably silk screen print method is used.

Silk screen print method is the one of porous printing, is the print process of the mesh of the screen cloth that make use of the fibers such as silk, nylon, Supreme Being's Telon or Stainless Steel Wire, relief printing plate, flat board, intaglio plate, curved surface can prints, may be used in a lot of field.By using silk screen print method, even just also above-mentioned surface protection curable resin composition can not can be coated with offsetting by fine fraction, be desirable in operability.

In the present invention, the material for processed component is not particularly limited.As this kind of material, such as, can enumerate the hardwares such as aluminium, iron, SUS, nickel; Glass component; The ceramic component such as aluminum oxide, aluminium nitride; Plastic member; The wafer such as silicon, sapphire.

The stripping means of protective membrane of the present invention can be applied to in the processing of the metal sheet being processed as representative of the opticses such as glass lens, plastic lens, glass or quartz, CD, mould, aluminium frame, plastic plate, semiconductor wafer, circuit substrate, pottery, sensor electronics, electric component.

Particularly as must prevent from cutting water enter or the stripping means of the damage of cutting swarf etc. or the protective membrane of the processed component such as the sensor element of pollution, the irregular circuit substrate of surperficial tool very useful.

In addition, to the preventing of the pollution caused by plating liquid used in the circuit substrates such as printed-wiring board (PWB), to the application such as scale, decoration of the various label such as nameplate, mark being not limited to implement in the various Industrial products of electronics, electric component, measuring instrument, that lettering adds sheltering of man-hour is very useful.

Embodiment

Below, utilize embodiments of the invention, comparative example is described in more detail, but they are not explained being construed as limiting property of the present invention.

(use material)

For material used in embodiment, comparative example, illustrate as follows.

I-907:2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino propane-1-ketone (Ciba Specialty Chemicals's system, " IRGACURE 907 ")

QM: methacrylic acid dicyclopentenyl oxygen base ethyl ester (Rohm & Hass Inc., " QM-657 ")

BZ: benzyl methacrylate (chemical company of common prosperity society system, " Light Ester BZ ")

IBX: isobornyl methacrylate (chemical company of common prosperity society system, " Light Ester IB-X ")

2-HEMA: 2-hydroxyethyl methacrylate

MTEGMA: methoxyl group Tetraglycol 99 monomethacrylates (chemical company of Xin Zhong village system, " NK Ester M-90G ")

TPO:2,4,6-trimethyl benzoyl diphenyl base phosphine oxide (BASF AG's system, LucirinTPO)

UC-203: methacryl-modified polyisoprene (Kuraray Inc., " UC-203 ")

TE-2000:1,2-polybutadiene ends urethane methacrylate (Japanese Cao Da Inc., " TE-2000 ", molecular weight 2000)

UV7000B: urethane acrylate (Japanese synthetic chemistry Inc., " purple light UV-7000B ", molecular weight 3500)

UV3000B: Polyester urethane acrylate (Japanese synthetic chemistry Inc., " purple light UV-3000B ", molecular weight 18000)

M-101A: phenolethylene oxide 2 mole acrylate (East Asia Synesis Company system, " Aronix M-101A ")

M-140:2-(1,2-hexamethylene carboxylic imide) ethyl propylene acid esters (East Asia Synesis Company system, " Aronix M-140 ")

IBXA: isobornyl acrylate (chemical company of common prosperity society system, " Light Acrylate IB-XA ")

R-684: Tricyclodecane Dimethanol diacrylate (Japanese chemical drug Inc., " KAYARAD R-684 ")

ACMO: acryloyl morpholine (Xing Ren Inc., " ACMO ")

BDK: benzil dimethyl ketal

MDP:2,2-methylene radical-bis-(4-methyl-6-tert-butylphenol)

Quintone 1700: cyclopentadiene resin (Nippon Zeon's system, " Quintone 1700 ")

Aerosil R972:Aerosil (Japanese Aerosil Inc.)

IPA: Virahol

(evaluation method)

Viscosity: using Brookfield viscometer, is under the condition of 23 DEG C in temperature, the viscosity of the curable resin composition of the surface protection made by mensuration.

Surface cure: on heat-resisting Pyrex (registered trademark) glass, utilizes silk screen print method to be coated with the curable resin composition of the surface protection prepared in advance with the coating thickness of about 70 μm.Then, the solidification equipment employing the Eyegraphics Inc. of metal halide lamp is utilized, at the integrating light quantity 2000mJ/cm of 365nm wavelength ²condition under make it solidify.Thereafter, use finger contact immediately, evaluate surface cure according to the determinating reference shown in following.

Zero: be not clamminess, well.

△: be slightly clamminess.

×: be clamminess, finger tip is contaminated.

Tensile shear bonding strength: measure according to JIS K 6850.Specifically, as adhesion material, use heat-resisting Pyrex (registered trademark) glass (25mm × 25mm × thick 2.0mm).The diameter of bonding site is set to 8mm, utilizes the curable resin composition prepared in advance, 2 heat-resisting Pyrex (registered trademark) glass are fitted mutually.Then, the solidification equipment employing the Fusion Inc. of electrodeless discharge lamp is utilized, at the integrating light quantity 2000mJ/cm of 365nm wavelength ²condition under solidified, make tensile shear bonding strength test film.To made test film, use universal testing machine, under the environment of temperature 23 DEG C, humidity 50%, measure tensile shear bonding strength with the draw speed of 10mm/min.

Stripping test (1): on heat-resisting Pyrex (registered trademark) glass, is coated with the curable resin composition prepared in advance.Then, the solidification equipment employing the Fusion Inc. of electrodeless discharge lamp is utilized, at the integrating light quantity 2000mJ/cm of 365nm wavelength ²condition under solidification compound is solidified, make the stripping test body as protective membrane.The test body of gained be impregnated in warm water (80 DEG C); took out every 5 minutes; protective membrane is being attached to gummy adhesive tape (the Denki Kagaku Kogyo kabushiki's system as thin slice; " Kararian Tape ") after; gummy adhesive tape is divested, measures the time that protective membrane is peeled off from heat-resisting Pyrex (registered trademark) glass.

Stripping test (2): except using except polycarbonate as adherend, make the stripping test body being formed with protective membrane in the same manner as stripping test (1).The time that protective membrane peels off from polycarbonate is similarly measured to the test body of gained.

(embodiment 1-1)

As (A) multifunctional (methyl) acrylate, coordinate the TE-2000 of 20 mass parts, the R-684 of 15 mass parts, as (B) simple function (methyl) acrylate, coordinate the M-140 of 40 mass parts, the M-101A of 25 mass parts, (A) and (B) are added up to the Quintone 1700 as (C) with the resin of cyclopentadienyl skeleton of 100 mass parts and 1 mass parts, the BDK as (D) Photoepolymerizationinitiater initiater of 10 mass parts, the IPA as (E) polar organic solvent of 2 mass parts, the MDP as polymerization retarder of 0.1 mass parts coordinates, preparation curable resin composition.Use the curable resin composition of gained, utilize above-mentioned shown evaluation method to carry out mensuration and the stripping test of the tensile shear bonding strength of its cured body.Their result is shown in table 1-1.

(embodiment 1-2 ~ 1-21)

Except using except the starting material of kind shown in table 1-1, table 1-2 to show the composition shown in 1-1, table 1-2, prepare curable resin composition in the same manner as embodiment 1-1.For the curable resin composition of gained, carry out mensuration and the stripping test of tensile shear bonding strength in the same manner as embodiment 1-1.Their result is shown in table 1-1, table 1-2.

[table 1-1]

) film like: the adhesive composite that have cured does not have slurries to peel off from glass surface with film like residually.

) slurries remain: have uncured caking agent at cured article remained on surface.

[table 1-2]

Slurries remain: have uncured caking agent at cured article remained on surface.

Film like: the adhesive composite that have cured does not have slurries to peel off from glass surface with film like residually.

(comparative example 1-1 ~ 1-6)

Except using except the starting material of kind shown in table 1-3 to show the composition shown in 1-3, prepare curable resin composition in the same manner as embodiment 1-1.For the curable resin composition of gained, carry out mensuration and the stripping test of tensile shear bonding strength in the same manner as embodiment 1-1.Their result is shown in table 1-3.

[table 1-3]

) slurries remain: although glass peel off, remain the adhesive composite that have cured at glass surface.

(embodiment 1-22)

Use the curable resin composition of embodiment 1-1, utilize the solidification equipment employing the Fusion Inc. of electrodeless discharge lamp, the integrating light quantity of 365nm wavelength is changed into 500,1000,2000,4000mJ/cm ²and curable resin composition is solidified, make stripping test body, tensile shear bonding strength test film, in addition, carry out mensuration and the stripping test of tensile shear bonding strength in the same manner as embodiment 1-1.Their result is shown in table 1-4.

(comparative example 1-7)

Use the curable resin composition of comparative example 1-6, utilize the solidification equipment employing the Fusion Inc. of electrodeless discharge lamp, the integrating light quantity of the wavelength of 365nm is changed into 500,1000,2000,4000mJ/cm ²and curable resin composition is solidified, make stripping test body, tensile shear bonding strength test film, in addition, carry out mensuration and the stripping test of tensile shear bonding strength in the same manner as embodiment 1-1.Their result is shown in table 1-4.

[table 1-4]

(embodiment 1-23,1-24)

Use the curable resin composition of embodiment 1-1 and embodiment 1-7, make stripping test body in the same manner as embodiment 1-1, the temperature of warm water is changed into 40 DEG C, 50 DEG C, 60,70 DEG C, carry out stripping test.The results are shown in table 1-5.Consequently, at any temperature, all there is separability.

[table 1-5]

	Resin combination NO.	Warm water temperature (DEG C)	40	50	60	70
							Embodiment 1-23	Embodiment 1-1	Splitting time (minute)	375	222	185	75
Embodiment 1-24	Embodiment 1-7	Splitting time (minute)	192	143	90	70

(embodiment 2-1)

As (A) multifunctional (methyl) acrylate, coordinate the R-684 of the TE-2000 of 20 mass parts, 15 mass parts, as (B) simple function (methyl) acrylate, coordinate n-acryloyl-oxyethyl hexahydrophthalic phthalimide (East Asia Synesis Company system of 40 mass parts, " Aronix M-140 ", hereinafter referred to as " M-140 ".), the M-101A of 25 mass parts, (A) and (B) are added up to 100 mass parts and 20 mass parts as (C), there is the BDK as (D) Photoepolymerizationinitiater initiater, the IPA as (E) polar organic solvent of 2 mass parts of Quintone 1700,10 mass parts of the resin of cyclopentadienyl skeleton, the MDP as polymerization retarder of 0.1 mass parts coordinates, preparation curable resin composition.Use the curable resin composition of gained, utilize above-mentioned shown evaluation method to carry out the mensuration of tensile shear bonding strength, viscosity, surface cure and stripping test.Their result is shown in table 2-1.

(embodiment 2-2 ~ 2-10)

Except using except the starting material of kind shown in table 2-1 to show the composition shown in 2-1, prepare curable resin composition in the same manner as embodiment 2-1.For the curable resin composition of gained, carry out mensuration and the stripping test of tensile shear bonding strength in the same manner as embodiment 2-1.Their result is shown in table 2-1.

[table 2-1]

(comparative example 2-1 ~ 2-5)

Except using except the starting material of kind shown in table 2-1 to show the composition shown in 2-1, prepare curable resin composition in the same manner as embodiment 2-1.To the curable resin composition of gained, carry out mensuration and the stripping test of tensile shear bonding strength in the same manner as embodiment 2-1.Their result is shown in table 2-2.

[table 2-2]

Consequently, the protective membrane formed by the curable resin composition of comparative example 2-1 and comparative example 2-5 is not peeled off from glass.In addition, the protective membrane formed by the curable resin composition of comparative example 2-2 and comparative example 2-4 dissolves while contacting with warm water, therefore fails to carry out utilizing the stripping test of thin slice.In addition, the protective membrane formed by the curable resin composition of comparative example 2-3 after the stripping test having carried out utilizing thin slice, a part of protective membrane residual (slurries remain).

(embodiment 2-11,2-12)

Use the curable resin composition of embodiment 2-1 and embodiment 2-5, make stripping test body in the same manner as embodiment 2-1, the temperature of warm water is changed into 40 DEG C, 50 DEG C, 60,70 DEG C, carry out stripping test.The results are shown in table 2-3.

[table 2-3]

	Resin combination No	Warm water temperature (DEG C)	40	50	60	70
							Embodiment 2-11	Embodiment 2-1	Splitting time (minute)	40	35	22	18
Embodiment 2-12	Embodiment 2-5	Splitting time (minute)	20	18	15	7

(embodiment 2-13)

Use the curable resin composition of embodiment 2-1, make stripping test body in the same manner as embodiment 2-1.Then, be used as the dicing tape (Denki Kagaku Kogyo kabushiki's system, " Elegrip ") of energy ray-curable caking agent as thin slice, after having irradiated ultraviolet, also carry out stripping test in the same manner as embodiment 2-1.Consequently, the curable resin composition of embodiment 2-1 and dicing tape are integrally peeled off.

(comparative example 2-6)

Use the curable resin composition of comparative example 2-1, make stripping test body in the same manner as embodiment 2-1.Then, use as the dicing tape (Denki Kagaku Kogyo kabushiki's system, " Elegrip ") of energy ray-curable caking agent is as thin slice, after having irradiated ultraviolet, also carry out stripping test in the same manner as embodiment 2-1.Consequently, the curable resin composition of comparative example 2-1 is unstripped.

(embodiment 2-14)

The curable resin composition of embodiment 2-1 is coated the silicon wafer of diameter 6 inches, solidified in the same manner as embodiment 2-1, thus form protective membrane.Then, fix in protection face side with dicing tape, use dicing device to be cut into 10mm square.Now, in cutting, there is not silicon wafer come off, do not cut water in addition yet and enter, show good processibility.Thereafter, irradiation ultraviolet radiation, reclaims this cutting test sheet.The protective membrane of all test films is all integrated with dicing tape, can reclaim the cutting test sheet not having protective membrane.

(comparative example 2-7)

The curable resin composition of comparative example 2-1 is coated the silicon wafer of diameter 6 inches, solidified in the same manner as embodiment 2-1, thus form protective membrane.Then, dicing device is used to be cut into 10mm in the same manner as embodiment 2-14 square.Now, in cutting, there occurs silicon wafer come off, in addition, confirm have protective membrane to dissolve, cut water and enter.Thereafter, irradiation ultraviolet radiation, reclaims this cutting test sheet.Residual protective membrane slurries in the test film of part.

(embodiment 3-1)

Using 80 mass parts as (F): on the end or side chain of molecule, there is more than one (methyl) acryl and the UC-203 of molecular weight (methyl) acrylate more than 500; 20 mass parts as (G): the QM of (methyl) acrylate beyond (F); 10 mass parts as (D): the I-907 of Photoepolymerizationinitiater initiater; 2 mass parts as (H): the Aerosil R972 belonging to drying process silicon-dioxide of inorganic filling material; The MDP as polymerization retarder of 0.1 mass parts coordinates, the curable resin composition of preparation surface protection.Use the curable resin composition of the surface protection of gained, utilize above-mentioned shown evaluation method to carry out mensuration and the stripping test of tensile shear bonding strength.Their result is shown in table 3-1.

(embodiment 3-2 ~ 3-19)

Except using except the starting material of kind shown in table 3-1, table 3-2 to show the composition shown in 3-1, table 3-2, prepare the curable resin composition of surface protection in the same manner as embodiment 3-1.To the curable resin composition of gained, carry out mensuration and the stripping test of tensile shear bonding strength in the same manner as embodiment 3-1.Their result is shown in table 3-1,3-2.

[table 3-1]

[table 3-2]

(comparative example 3-1 ~ comparative example 3-5)

Except employing except the starting material of kind shown in table 3-3 to show the composition shown in 3-3, prepare curable resin composition in the same manner as embodiment 3-1.To the curable resin composition of gained, carry out viscosimetric analysis in the same manner as embodiment 3-1.

Utilize silk screen print method in the same manner as embodiment 3-1, carry out the making of the test film of surface cure and stripping test.But the viscosity of comparative example 3-1 ~ 3-5 is all low, fail to carry out silk screen printing.So, utilizing and brush, being coated with curable resin composition as on heat-resisting Pyrex (registered trademark) glass of adherend, polycarbonate, carrying out surface cure and stripping test.Their result is shown in table 3-3.

[table 3-3]

Consequently, the curable resin composition of the surface protection of embodiment 3-1 ~ 3-19 can carry out silk screen printing, guarantees surface cure, and the protective membrane of gained is all easy to peel off with film like.

The protective membrane formed by the curable resin composition of comparative example 3-1 and comparative example 3-5 is not all peeled off from the arbitrary adherend glass, polycarbonate.

In addition, the protective membrane formed by the curable resin composition of comparative example 3-2 and comparative example 3-4 dissolves while contacting with warm water.In addition, the protective membrane formed by the curable resin composition of comparative example 3-3 is after carrying out stripping test, and a part of protective membrane remains (slurries remain).

Resin combination of the present invention has light solidified, and its cured body can not embody high-adhesive-strength by cutting water etc. with affecting, and therefore not easily produces offsetting man-hour in adding of processed component, can obtain tool member excellent in dimensional precision easily.In addition, reducing bonding strength by contacting with warm water, component can be reclaimed easily, can use as the temporary fixed caking agent of optical lens, prism, array, silicon wafer, semi-conductor installation parts etc.

In addition; the present invention is so a kind of stripping means: in the processing of optics or sensor electronics, electric component; particularly in precision sizing such as cutting, grinding, grinding etc.; the position for the protection of the machined surface of this processed component or circuit, sensor site etc. with function to be entered or the damage of cutting swarf etc. or the protective membrane of pollution are peeled off from processed component from cutting water; easy and do not have slurries remain; Environmental also excellent, industrially very useful.

In addition, the present invention may be used for the protective membrane preventing the pollution caused by plating liquid used in the circuit substrates such as printed-wiring board (PWB); Sheltering of man-hour is added to application, the lettering such as scale, decoration of the various label such as nameplate, mark being not limited to implement in the various Industrial products of electronics, electrical component, measuring instrument.

Quote the full content of the specification sheets of No. 2006-005597, the Japanese patent application of application on January 13rd, 2006, No. 2006-248859, the Japanese patent application of application on September 14th, 2006 and No. 2006-281257, the Japanese patent application of application on October 16th, 2006, claims and summary here, the disclosure as specification sheets of the present invention is introduced.

Claims (2)

1. the method for temporarily fixing of a processed component, it is characterized in that, use the curable resin composition of surface protection that processed component is adhered to base material, and after described curable resin composition is solidified, after this processed component is processed, impregnated in the warm water of 30 DEG C ~ 90 DEG C, take off the cured body of the curable resin composition of described surface protection, the curable resin composition of described surface protection contains (A): have hydrophobic multifunctional (methyl) acrylate, (B): there is hydrophobic simple function (methyl) acrylate, (C): there is cyclopentadienyl skeleton and there is the resin of ester group or hydroxyl in molecule, (D): Photoepolymerizationinitiater initiater,

Described (A): there is hydrophobic multifunctional (methyl) acrylate; be in oligopolymer/polymer end or side chain more than 2 by (methyl) acrylated multifunctional (methyl) origoester acrylate/polymer or the monomer with more than 2 (methyl) acryls

In total amount 100 mass parts of (A) and (B), (A) containing 1 ~ 50 mass parts, (B) of 5 ~ 95 mass parts, contain (C) of 0.1 ~ 50 mass parts, (D) of 0.1 ~ 20 mass parts relative to total amount 100 mass parts of (A) and (B).

2. the method for temporarily fixing of a processed component, it is characterized in that, use the curable resin composition of surface protection that processed component is adhered to base material, and after described curable resin composition is solidified, after this processed component is processed, impregnated in the warm water of 30 DEG C ~ 90 DEG C, take off the cured body of the curable resin composition of described surface protection, the curable resin composition of described surface protection contains (A): have hydrophobic multifunctional (methyl) acrylate, (B): there is hydrophobic simple function (methyl) acrylate, (C): there is cyclopentadienyl skeleton and there is the resin of ester group or hydroxyl in molecule, (D): Photoepolymerizationinitiater initiater, (E) polar organic solvent,

Described (A): there is hydrophobic multifunctional (methyl) acrylate; be in oligopolymer/polymer end or side chain more than 2 by (methyl) acrylated multifunctional (methyl) origoester acrylate/polymer or the monomer with more than 2 (methyl) acryls

In total amount 100 mass parts of (A) and (B), (A) containing 1 ~ 50 mass parts, (B) of 5 ~ 95 mass parts, contain (C), (D) of 0.1 ~ 20 mass parts, (E) of 0.5 ~ 10 mass parts of 0.1 ~ 50 mass parts relative to total amount 100 mass parts of (A) and (B).