Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F

Definitions

• the present invention relates to a composition for use in temporary fixation.
• inorganic materials such as silicon are used as substrates.
• Wafer-type substrates with a thickness of several hundred microns are often used, which are obtained by processing the surface of the substrate through processes such as forming an insulating film, forming circuits, and thinning by grinding.
• measures to prevent damage are necessary, especially when thinning by grinding.
• the conventional method for preventing this is to apply a temporary protective tape to the surface opposite the surface to be ground (also called the back surface), which can be peeled off after the processing process is completed.
• This tape uses an organic resin film as the base material, and while it is flexible, it lacks strength and heat resistance, making it unsuitable for use in high-temperature processes.
• a system has been proposed that provides sufficient durability to withstand the process conditions of back grinding and back electrode formation by bonding electronic device substrates to a support such as silicon or glass via an adhesive. What is important here is the adhesive layer used when bonding the substrate to the support. This must be able to bond the substrate to the support without any gaps and must be durable enough to withstand subsequent processes, and finally, the thinned wafer must be easily peeled off from the support, i.e., temporarily fixed.
• the main processes for processing such wafers are spin coating, vacuum bonding and light curing, thinning by grinding and polishing, high-temperature treatment, laser peeling, and temporary fixing agent removal.
• the temporary fixative In the spin coating process, the temporary fixative must have an appropriate viscosity and be a Newtonian fluid (or have a shear viscosity that is independent of shear rate) so that a uniform film of the temporary fixative can be formed on the wafer.
• the temporary fixative In the vacuum bonding/UV curing process, the temporary fixative must be able to cure in a short time on a support such as glass by exposure to ultraviolet (UV) light, and must generate minimal outgassing (low outgassing).
• UV ultraviolet
• the temporary fixative In the thinning process using grinding and polishing, to avoid damage caused by the load of the grinding machine being applied locally to the substrate, the temporary fixative must have an appropriate hardness to distribute the load in the in-plane direction while preventing localized sinking of the substrate and maintaining flatness. In addition, the temporary fixative must also have adhesion to the support, an appropriate elastic modulus to protect the edges, and chemical resistance.
• the temporary fixative In the high-temperature treatment process, the temporary fixative must be heat-resistant enough to withstand long periods of high-temperature treatment in a vacuum (for example, at 300°C or higher for one hour or more).
• the temporary fixative is required to be able to be peeled off quickly using a laser such as a UV laser.
• the adhesive In the removal process, in addition to easy peelability so that the substrate can be easily peeled off from the support, the adhesive must also have cohesive properties so that no adhesive residue remains on the substrate after peeling, and be easy to clean.
• Patent Document 1 discloses a temporary fixing composition that contains (A-1) a monofunctional (meth)acrylate whose side chain is an alkyl group having 18 or more carbon atoms and whose homopolymer has a Tg of -100°C to 60°C, (A-2) a polyfunctional (meth)acrylate, (B) a polyisobutene homopolymer and/or a polyisobutene copolymer, and (C) a photoradical polymerization initiator, and claims that the composition has excellent heat resistance, low outgassing properties, and peelability.
• A-1 a monofunctional (meth)acrylate whose side chain is an alkyl group having 18 or more carbon atoms and whose homopolymer has a Tg of -100°C to 60°C
• A-2 a polyfunctional (meth)acrylate
• B a polyisobutene homopolymer and/or a polyisobutene copolymer
• C a
• Patent Document 2 also discloses a method for producing a laminate including a light-to-heat conversion layer that contains a light absorber such as carbon black and a thermally decomposable resin, for use in producing a thinned substrate.
• a light absorber such as carbon black
• a thermally decomposable resin for use in producing a thinned substrate.
• Patent Document 1 discloses that a UV absorbent can be added. However, depending on the application, such as when it is necessary to suppress heat generation due to light irradiation, it may be necessary to incorporate a relatively large amount of UV absorbent, but UV absorbents are generally poorly soluble solids. Patent Document 1 does not mention that even if the amount of UV absorbent is increased, it is unlikely to cause problems with compatibility with other raw materials.
• Patent Document 2 involves the carbon black in the light-to-heat conversion layer generating heat, which decomposes the thermally decomposable resin and reduces the peeling force, but this inevitably generates a large amount of heat, which can have a negative effect on products that are sensitive to heat.
• the present invention was made in consideration of the above problems, and aims to provide a temporary fixing composition that has long-term availability and can be formulated with a sufficient amount of UV absorbent for temporary fixing applications.
• the present invention provides the following aspects.
• Aspect 1 (A) a first (meth)acrylate monomer; (B) a photoradical polymerization initiator; (C) a UV absorber,
• the component (A) is (A-1) a monofunctional (meth)acrylate monomer, and (A-2) a polyfunctional (meth)acrylate monomer,
• the absolute value of the difference between the ⁇ P of component (A) and the ⁇ P of component (C) is 5 or less;
• the dispersion term ⁇ D at 25°C among the Hansen solubility parameters the ⁇ D of component (A) is 16 or more and 20 or less;
• the composition, wherein the Hansen solubility parameter is calculated by converting a molecular structure into a SMILES notation using HSPiP (Hansen Solubility Parameters in Practice) software.
• composition according to claim 1 or 2 wherein the monofunctional (meth)acrylate monomer has an aromatic ring.
• Aspect 4 further comprising a (meth)acrylate polymer,
• ⁇ P at 25°C of the Hansen solubility parameters the absolute value of the difference between the ⁇ P of component (D) and the ⁇ P of component (C) is 5 or less;
• (E) a second (meth)acrylate monomer, Regarding the polarity term ⁇ P at 25 ° C. of the Hansen solubility parameters, the absolute value of the difference between the ⁇ P of the component (E) and the ⁇ P of the component (C) is greater than 5; or, regarding the dispersion term ⁇ D at 25 ° C. of the Hansen solubility parameters, the ⁇ D of the component (E) is less than 16 or greater than 20,
• Aspect 6 A composition according to any one of aspects 1 to 5, wherein the component (C) has one or more polymerizable functional groups per molecule.
• Aspect 7 The composition according to any one of aspects 1 to 6, wherein the amount of the component (C) is 1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the entire composition excluding the components (C) and (B).
• Aspect 9 The composition according to any one of Aspects 1 to 8, wherein the composition is formulated in a light-shielding container at 70° C., allowed to stand until the temperature reaches 23° C., and then stored in a thermostatic chamber at 15° C. for 3 days, and does not cause precipitation.
• Aspect 10 (A) a first (meth)acrylate monomer including at least a monofunctional (meth)acrylate monomer; (B) a polymerization initiator; (C) a UV absorber,
• the component (A) is (A-1) Contains a monofunctional (meth)acrylate monomer,
• a composition comprising:
• the present invention has the effect of being able to incorporate a sufficient amount of UV absorbent with long-term availability for temporary fixing applications.
• a monofunctional (meth)acrylate refers to a compound having one (meth)acryloyl group in one molecule.
• a polyfunctional (meth)acrylate refers to a compound having two or more (meth)acryloyl groups in one molecule.
• An n-functional (meth)acrylate refers to a compound having n (meth)acryloyl groups in one molecule.
• the polymerizable functional group in a polyfunctional (meth)acrylate may have only an acryloyl group, may have only a methacryloyl group, or may have both an acryloyl group and a methacryloyl group.
• the notation such as "C 1 to C 20 " or "C 10 to C 20 " means a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 10 to 20 carbon atoms.
• a photocurable composition in one embodiment, contains (A) a first (meth)acrylate monomer containing at least a monofunctional (meth)acrylate monomer, (B) a polymerization initiator, preferably a photoradical polymerization initiator, and (C) a UV absorber, and preferably has Hansen Solubility Parameters that satisfy a predetermined condition.
• this photocurable composition may be simply referred to as a "composition” or a “temporary fixing agent.”
• a cured product obtained by curing the composition can be provided, and the curing can be performed with light (e.g., ultraviolet light) having a wavelength corresponding to the (B) component and/or the (C) component.
• the Hansen solubility parameters of the curable composition are calculated using HSPiP (Hansen Solubility Parameters in Practice) software by setting the measurement temperature at 25°C and converting the target molecular structure formula using the SMILES notation (hereinafter the same applies unless otherwise specified).
• HSPiP Hanesen Solubility Parameters in Practice
• the HSPiP software is available from the official website below. https://www. hansen-solubility. com/downloads. php
• the Hansen solubility parameter has the following three components: ⁇ D : Dispersion term (van der Waals force) ⁇ P : polar term ⁇ H : hydrogen bond term
• ⁇ D Dispersion term (van der Waals force)
• ⁇ P polar term
• ⁇ H hydrogen bond term
• the absolute value of the difference between the ⁇ P of component (A) and the ⁇ P of component (C) must be 5 or less, and the ⁇ D of component (A) must be 16 to 20. This provides an effect of suppressing the undesired precipitation of component (C). It is also acceptable for the present composition to contain multiple types of a certain component. Naturally, in this case, each of the multiple types must satisfy the above conditions regarding the Hansen solubility parameters.
• the ⁇ P of the component (A) is preferably 1.5 to 11.5, 2.0 to 11.0, 2.5 to 10.5, or 3.0 to 10.0.
• the ⁇ H of the component (A) is preferably from 2.5 to 7.5, from 3.0 to 7.0, from 3.5 to 6.5, or from 4.0 to 6.0.
• the (meth)acrylate monomer which is component (A) contained in this composition, can be appropriately selected in consideration of the Hansen solubility parameter depending on the component (C) used in combination.
• Component (A) contains at least monofunctional (meth)acrylate monomer (A-1) and polyfunctional (meth)acrylate monomer (A-2).
• the component (A-1) may include any monofunctional (meth)acrylate monomer, and preferably an aromatic monofunctional (meth)acrylate monomer may be used.
• aromatic monofunctional (meth)acrylate include C 1 -C 20 alkylphenol (meth)acrylate and C 1 -C 20 alkylphenol EO (ethylene oxide) modified (meth)acrylate.
• the (A-2) component may include any difunctional or higher (meth)acrylate monomer.
• the difunctional (meth)acrylate monomer may include, for example, an aromatic difunctional (meth)acrylate and/or an aliphatic difunctional (meth)acrylate.
• the aromatic difunctional (meth)acrylate can be added to the composition so as to form a rigid skeleton.
• the rigidity can be further increased.
• aromatic difunctional (meth)acrylates include 9,9-bis[4-(2-hydroxy C 1 -C 20 alkoxy)phenyl]fluorene di(meth)acrylate, C 1 -C 20 alkoxylated bisphenol A di(meth)acrylate, benzyl di(meth)acrylate, 1,3-bis(2-(meth)acryloyloxy C 1 -C 20 alkyl)benzene, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, or structural isomers thereof.
• di(meth)acrylates having a condensed ring skeleton such as a fluorene, indene, indecene, anthracene, azulene, or triphenylene skeleton may be included.
• Examples of aliphatic difunctional (meth)acrylates include C 1 -C 20 alkyl diol di(meth)acrylates .
• Examples of 20 alkyl diol di(meth)acrylate include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol modified trimethylolpropane di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 2,2-bis(4-(meth)acryloxypropoxyphenyl)propane, 2,2-bis(4-
• aliphatic difunctional (meth)acrylate examples include C 1 to C 20 alkoxylated hydrogenated bisphenol A di(meth)acrylate (including alkylene oxide modified hydrogenated bisphenol A di(meth)acrylate), 1,3-di(meth)acryloyloxyadamantane, tricyclo C 10 to C 20 alkane dimethanol di(meth)acrylate (e.g. tricyclodecane dimethanol di(meth)acrylate, etc.), dicyclo C 5 to C 20 di(meth)acrylate, or structural isomers thereof.
• alkoxylated hydrogenated bisphenol A di(meth)acrylate including alkylene oxide modified hydrogenated bisphenol A di(meth)acrylate), 1,3-di(meth)acryloyloxyadamantane
• tricyclo C 10 to C 20 alkane dimethanol di(meth)acrylate e.g. tricyclodecane dimethanol di(meth)acrylate, etc.
• trifunctional (meth)acrylates include ethylene oxide-modified isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and tris[(meth)acryloyloxyethyl]isocyanurate.
• tetrafunctional or higher (meth)acrylates examples include ditrimethylolpropane tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.
• a composition can be provided that contains a combination of an aromatic monofunctional (meth)acrylate as component (A-1) and an aromatic difunctional (meth)acrylate as component (A-2).
• this composition contains this combination after adjusting the Hansen solubility parameter taking into account component (C), it is possible to obtain the effect of making it easier to suppress precipitation of component (C).
• component (A) is preferably 45 to 75 parts by mass, 45.0 to 75.0 parts by mass, 47.5 to 72.5 parts by mass, 50 to 70 parts by mass, or 50.0 to 70.0 parts by mass, where the total amount of the composition excluding components (C) and (B) is 100 parts by mass.
• the content of component (A-1) is preferably 2.5 to 35 parts by mass, 2.5 to 35.0 parts by mass, 5 to 30 parts by mass, 5.0 to 30.0 parts by mass, or 7.5 to 27.5 parts by mass, where the total amount of the composition excluding components (C) and (B) is 100 parts by mass.
• the content of the (A-2) component is preferably 10 to 60 parts by mass, 10.0 to 60.0 parts by mass, 15 to 55 parts by mass, 15.0 to 55.0 parts by mass, or 17.5 to 52.5 parts by mass, where the total amount of the composition excluding the (C) and (B) components is 100 parts by mass.
• the polymerization initiator which is the component (B) contained in the present composition, and preferably a photoradical polymerization initiator, is a substance that can initiate radical polymerization of the component (A) (and other monomers contained as necessary) upon irradiation with light, and refers to, for example, a compound whose molecules are cleaved and split into two or more radicals upon irradiation with ultraviolet light or visible light (e.g., wavelength 350 to 700 nm, preferably 365 to 500 nm, more preferably 385 to 450 nm).
• ultraviolet light or visible light e.g., wavelength 350 to 700 nm, preferably 365 to 500 nm, more preferably 385 to 450 nm.
• photoradical polymerization initiator examples include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis( ⁇ 5 -2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime
• the (B) component may preferably contain an acylphosphine oxide-based compound.
• acylphosphine oxide-based compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• As a photoradical polymerization initiator it is preferable that it is highly sensitive, has excellent deep curing properties due to its photofading resistance, and has an absorption wavelength range for generating radicals that extends to a relatively long wavelength range.
• the absorption wavelength range is in the range of wavelengths up to about 440 nm, which is significantly different from the absorption wavelength range of the UV absorber used in the UV laser peeling process described below.
• the degree of UV curing inhibition by the UV absorber is small, and radical polymerization can be initiated with light of a longer wavelength. Therefore, even in the presence of a UV absorber, the effect of initiating radical polymerization and curing efficiently at a relatively high speed can be obtained.
• the photoradical polymerization initiator can be selected based on absorbance.
• the photoradical polymerization initiator can be selected from one or more compounds that, when dissolved at a concentration of 0.1% by mass in a solvent (e.g., acetonitrile or toluene) that does not have a maximum absorption in the wavelength region of 300 to 500 nm, satisfy one or more of the following conditions: absorbance at a wavelength of 365 nm is 0.5 or more, absorbance at a wavelength of 385 nm is 0.5 or more, and absorbance at a wavelength of 405 nm is 0.5 or more.
• a solvent e.g., acetonitrile or toluene
• Examples of compounds that satisfy such conditions include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), which has an absorbance of 0.5 or more at a wavelength of 365 nm when dissolved at a concentration of 0.1% by mass in acetonitrile as a solvent; 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, which has an absorbance of 0.5 or more at wavelengths of 365 nm and 385 nm; and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, which have an absorbance of 0.5 or more at wavelengths of 365 nm, 385 nm, and 405 nm.
• bis( ⁇ 5 -2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium having an absorption wavelength range of 400 to 500 nm can also be used as a photoradical polymerization initiator.
• acylphosphine oxide compounds titanocene compounds, and ⁇ -aminoalkylphenone compounds are preferred in terms of reaction speed, heat resistance after curing, low outgassing, and absorption characteristics in a region different from the wavelength of the UV laser used in the UV laser peeling described below and the absorption wavelength region of the UV absorber used in the UV laser peeling.
• oxime ester compounds can also be selected as photoradical polymerization initiators for resin compositions for temporary fixing applications to prevent damage from bonding of the substrate to be processed to the support substrate until the heating step, which is not a layer for the UV laser peeling process, among the temporary fixing compositions having the structure described below.
• Acylphosphine oxide compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Among these, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is particularly preferred.
• titanocene compound is bis( ⁇ 5 -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium.
• ⁇ -aminoalkylphenone compounds examples include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, etc.
• Oxime ester compounds include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-O-benzoyloxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), etc. Among these, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) is preferred.
• the amount of (B) photoradical polymerization initiator used is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 1 part by mass, per 100 parts by mass of (A) component, in terms of reaction speed, heat resistance after curing, and low outgassing. If the amount of (B) component is 0.01 part by mass or more, sufficient curing properties are obtained, and if it is 5 parts by mass or less, the effect of low outgassing properties and heat resistance being less likely to be impaired is obtained.
• the UV absorber which is component (C) refers to a compound whose molecules are cut and decomposed/vaporized when irradiated with ultraviolet or visible light laser, and this decomposition/vaporization occurs at the interface between the support substrate (or support) and the temporary fixative, causing a loss of adhesion between the temporary fixative and the support substrate (or support) that had been maintained up until just before the peeling process.
• the UV absorbent one or more compounds selected from benzotriazole-based compounds and hydroxyphenyltriazine-based compounds are preferred in terms of the degree of overlap with the UV laser wavelength in the UV absorption wavelength region, UV absorption characteristics at the same wavelength, low outgassing properties, and heat resistance.
• the component (C) can be selected in consideration of the ⁇ P relationship with the component (A).
• the ⁇ P of the component (C) is preferably 3 to 10, 3.0 to 10.0, 3.5 to 9.5, 4 to 9, or 4.0 to 9.0.
• the amount of the UV absorber, which is component (C), is preferably 1 to 20 parts by mass, and more preferably 5 to 20 parts by mass, based on a total of 100 parts by mass of the entire composition excluding components (C) and (B).
• the present invention can contain a larger amount of UV absorber than the prior art. If the amount of component (C) is 1 part by mass or more, a sufficient UV laser peeling speed can be obtained, and if it is 20 parts by mass or less, the effect of low outgassing properties and heat resistance not being easily impaired can be obtained.
• the UV absorber may have one or more polymerizable functional groups (e.g., (meth)acryloyl groups, vinyl ether groups, ester groups, etc.) per molecule. If the UV absorber has a (meth)acryloyl group, the UV absorber is not considered to be component (A). The use of component (C) having such a polymerizable functional group has the effect of obtaining a more appropriate crosslinked structure.
• polymerizable functional groups e.g., (meth)acryloyl groups, vinyl ether groups, ester groups, etc.
• Benzotriazole compounds include 2-[2-hydroxy-5-[2-(meth)acryloyloxy)ethyl]phenyl]-2H-benzotriazole, 2,2'-dihydroxy-4,4'-di-2-(meth)acryloyloxyethoxybenzophenone, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1 ,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriazole are particularly preferred in terms of compatibility with the resin component,
• hydroxyphenyltriazine compound one or more selected from the group consisting of 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine are particularly preferred in terms of compatibility with component (A), UV absorption characteristics, low outgassing, and heat resistance.
• the composition may further include a (meth)acrylate polymer as component (D). It is preferable that the absolute value of the difference between ⁇ P of component (D) and ⁇ P of component (C) is 5 or less, and/or ⁇ D of component (D) is 16 to 20.
• (meth)acrylate polymers include (meth)acrylic polymers or (meth)acrylic copolymers having a (meth)acryloyl group in the side chain. Such polymers are available, for example, as the product name "Art Resin” series manufactured by Negami Chemical Industries Co., Ltd. and the product name "KANEKA XMAP” series manufactured by Kaneka Corporation.
• component (D) provides the effect of making it easier to adjust the rigidity and flexibility of the crosslinked structure formed when the composition is cured.
• the weight average molecular weight of the (D) component is preferably 5000 to 200000.
• a suitable viscosity can be obtained when blended with other polymerizable components.
• the weight average molecular weight of the (D) component is 10000 or more, a suitable thickening effect can be obtained.
• the weight average molecular weight of the (D) component is more preferably 6000 or more, and even more preferably 7000 or more.
• the weight average molecular weight of the (D) component is 200000 or less, good spin coatability with low shear rate dependency can be obtained.
• the weight average molecular weight of the (D) component is more preferably 190000 or less, even more preferably 180000 or less, even more preferably 150000 or less, and particularly preferably 100000 or less.
• the functional group equivalent weight of component (D) is preferably 500 to 20,000, more preferably 700 to 10,000, and most preferably 1,000 to 7,000.
• the amount of component (A) may be 50% by mass or more and 95% by mass or less, preferably 50% by mass or more and 90% by mass or less, and more preferably 50% by mass or more and 85% by mass or less, in terms of the mass ratio of components (A) and (D).
• the composition may further include a second (meth)acrylate monomer as component (E) different from component (A).
• the absolute value of the difference between ⁇ P of component (E) and ⁇ P of component (C) is greater than 5, or ⁇ D of component (E) is less than 16 or greater than 20.
• the composition does not include component (E), or when the total of components (A) and (E) is taken as 100% by mass, it is preferable that component (E) is 50% by mass or less, more preferably 40% by mass or less.
• component (E) include monofunctional alkyl (meth)acrylates, such as isostearyl (meth)acrylate.
• This composition does not require a separate adhesive layer and light-to-heat conversion layer as in Patent Document 2, and can function by forming only one layer. For this reason, it is preferable that this composition does not contain a filler such as carbon black.
• the UV transmittance of the cured product in this specification is a value obtained by reflectance measurement spectroscopy. Specifically, the transmittance is obtained under the following conditions using a film of the cured product with a thickness of approximately 50 ⁇ m, which is prepared by sandwiching the film between sheets of PET resin, and using a reflectance spectroscopy measuring device (V-650 manufactured by JASCO Corporation).
• the weight average molecular weight in this specification is a value calculated using standard polystyrene as measured by gel permeation chromatography (GPC). Specifically, the weight average molecular weight is determined under the following conditions using tetrahydrofuran as a solvent, a GPC system (Tosoh Corporation SC-8010), and a calibration curve created using commercially available standard polystyrene.
• GPC gel permeation chromatography
• the composition can be used as a temporary fixing resin composition, a temporary fixing adhesive, a pressure sensitive adhesive sheet, or a temporary fixing adhesive for electronic device manufacturing.
• the temporary fixing composition, the temporary fixing resin composition, and the temporary fixing adhesive are sometimes collectively referred to as a temporary fixing agent.
• the present composition When the present composition is used to bond a substrate to be processed and an optically transparent support substrate (or support), it is preferable to irradiate visible light or ultraviolet light (wavelength or central wavelength 365 to 405 nm) so that the energy amount is 1 to 20,000 mJ/cm 2. If the energy amount is 1 mJ/cm 2 or more, sufficient adhesion is obtained, and if it is 20,000 mJ/cm 2 or less, productivity is excellent, decomposition products from the photoradical polymerization initiator are unlikely to be generated, and outgassing is suppressed. In terms of productivity, adhesion, low outgassing, and easy peeling, it is preferable that the energy amount is 1,000 to 10,000 mJ/cm 2 .
• the substrates to be bonded with the present composition it is preferable that at least one of the substrates is a transparent substrate that transmits light.
• transparent substrates include inorganic substrates such as crystal, glass, quartz, calcium fluoride, and magnesium fluoride, and organic substrates such as plastics.
• inorganic substrates are preferable because of their versatility and the fact that they provide great effects.
• inorganic substrates one or more selected from glass and quartz are preferable.
• the composition may be photocurable, and the cured product provided thereby has excellent heat resistance and peelability.
• the cured product of the composition of the present invention has a low outgassing amount even when exposed to high temperatures, and is suitable for bonding, sealing, and coating various optical parts, optical devices, and electronic parts.
• the composition of the present invention is suitable for applications requiring a wide range of durability, such as solvent resistance, heat resistance, and adhesion, particularly for semiconductor manufacturing process applications.
• the cured product of this composition can be used in processes over a wide range of temperatures, from room temperature to high temperatures.
• the heating temperature during the process is preferably 350°C or less, more preferably 300°C or less, and most preferably 250°C or less.
• an adhesive in which a substrate is bonded using the composition as an adhesive.
• the adhesive can be peeled off by applying an external force.
• the adhesive can be peeled off by inserting a blade, sheet, or wire into the bonded portion.
• the adhesive can be peeled off by irradiating the entire surface of the adhesive on the optically transparent substrate side with a UV laser or IR laser in a scanning manner.
• the composition (before curing) is mixed in a light-shielding container at 70°C, allowed to cool to 23°C, and then stored in a thermostatic chamber at 15°C.
• the number of days during which no precipitation occurs is preferably 3 days or more, more preferably 4 days or more, even more preferably 7 days or more, and even more preferably 14 days or more.
• the composition is extremely resistant to precipitation.
• a storage method can be provided in which the composition is mixed in a light-shielding container at 70°C, allowed to cool to 23°C, and then stored in a thermostatic chamber at 15°C. The method can also provide a method for extending the storage period of the composition by adjusting the Hansen solubility parameters of each component.
• the unit of usage is parts by mass.
• A-BPEF-2 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate
• HBPE-4 EO-modified hydrogenated bisphenol A diacrylate
• HBPE-4" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., m + n ⁇
• A-DOD-N 1,10-decanediol diacrylate
• NK Ester A-DOD-N manufactured by Shin-Nakamura Chemical Co., Ltd.
• M-113 Nonylphenol EO modified acrylate ("Aronix M-113" manufactured by Toagosei Co., Ltd., n ⁇ 4)
• component (B) The following was used as component (B): I819: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BASF "Irgacure 819")
• RUVA-93 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., "RUVA-93")
• P-66 2,2'-dihydroxy-4,4'-di-2-acryloyloxyethoxybenzophenone (manufactured by Daiwa Kasei Co., Ltd., "Dynesorb P-66")
• APB-001 Polybutyl multifunctional acrylate polymer containing acryloyl groups in the side chains (“APB-001” manufactured by Negami Chemical Industries, Ltd., weight average molecular weight 72,000, functional group equivalent weight 1400)
• ISTA Isostearyl acrylate
• Comparative Examples 1 and 2 which did not contain component (A-1) and did not satisfy the Hansen solubility parameter conditions, were unsuitable because precipitation occurred on the same day or within two days.
• This composition can maintain its usability even after long-term storage even when a sufficient amount of UV absorbent is blended, and therefore has the remarkable effect of suppressing heat generation accompanying light irradiation during laser peeling by the UV absorbent.

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• 2024
  • 2024-01-22 JP JP2024574441A patent/JPWO2024162049A1/ja active Pending
  • 2024-01-22 WO PCT/JP2024/001552 patent/WO2024162049A1/ja not_active Ceased
  • 2024-01-22 CN CN202480008940.7A patent/CN120584140A/zh active Pending
  • 2024-01-25 TW TW113102914A patent/TW202436368A/zh unknown

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