WO2024038670A1 - Uv-curable silicone composition, cured product, and silicon wafer coating agent - Google Patents

Uv-curable silicone composition, cured product, and silicon wafer coating agent Download PDF

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WO2024038670A1
WO2024038670A1 PCT/JP2023/022591 JP2023022591W WO2024038670A1 WO 2024038670 A1 WO2024038670 A1 WO 2024038670A1 JP 2023022591 W JP2023022591 W JP 2023022591W WO 2024038670 A1 WO2024038670 A1 WO 2024038670A1
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curable silicone
component
silicone composition
group
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武春 豊島
利之 小材
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信越化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping

Definitions

  • the present invention relates to an ultraviolet curable silicone composition, a cured product, and a silicon wafer coating agent.
  • UV-curable silicone materials have a long pot life under light-shielded conditions, and also have the characteristic of rapidly curing even at room temperature after irradiation with UV rays, so they are effective, for example, in applications where they are cured on large-area substrates. be.
  • the manufacturing of semiconductor silicon involves hundreds of physical and chemical processing steps on silicon substrates, and defects such as cracks in the silicon substrate and scratches from excavated pieces can occur during processing. There are cases where Therefore, it is thought that the yield can be improved by using a coating agent that protects the silicon substrate during processing.
  • silicone rubber is flexible and has excellent mechanical strength, so it can prevent warping and cracking of the silicon substrate, and it also has excellent chemical resistance, so it is suitable for such coating agents. It is considered useful.
  • UV-curable silicone materials are considered to be useful from the viewpoint of pot life and curing speed. Conceivable.
  • Adhesive aids such as alkoxysilanes and epoxy group-containing compounds are generally added to silicone coating agents and silicone adhesives in order to impart adhesion to substrates.
  • these adhesion aid components may stick to the silicon substrate or processing equipment, and may cause contamination and equipment contamination.
  • the present invention was made in view of the above circumstances, and provides an ultraviolet curable silicone composition that adheres well to metal silicon without the addition of an adhesion aid such as an alkoxysilane or an epoxy group-containing compound.
  • an adhesion aid such as an alkoxysilane or an epoxy group-containing compound.
  • the present inventors discovered that a predetermined alkenyl group-containing organopolysiloxane, a predetermined linear organohydrogenpolysiloxane, and a predetermined linear organohydrogenpolysiloxane that can be activated by light with a wavelength of 200 to 500 nm.
  • the present invention was completed based on the discovery that a composition containing a platinum group metal catalyst adheres well to metallic silicon without the addition of an adhesion aid.
  • the present invention 1.
  • R 1 each independently represents an unsubstituted or substituted monovalent hydrocarbon group
  • A each independently represents an alkenyl group
  • m is an integer of 1 to 10,000.
  • an ultraviolet curable silicone composition 2.
  • a cured product of the ultraviolet curable silicone composition of 1 or 2 4.
  • a silicon wafer coating agent comprising one or two ultraviolet curable silicone compositions is provided.
  • the ultraviolet curable silicone composition of the present invention adheres well to metal silicon even without the addition of an adhesion aid such as an alkoxysilane or an epoxy group-containing compound.
  • an adhesion aid such as an alkoxysilane or an epoxy group-containing compound.
  • sufficient working time can be secured before irradiation with ultraviolet rays, and curing proceeds rapidly even at room temperature after irradiation with ultraviolet rays, making it suitable as a coating agent for silicon wafers.
  • the ultraviolet curable silicone composition according to the present invention contains the following components (A) to (C) as essential components.
  • Component (A) in the ultraviolet curable silicone composition of the present invention includes at least one of the following components (i) and (ii).
  • Component (i) is represented by the following formula (1), has at least two, preferably two, alkenyl groups bonded to a silicon atom in one molecule, and has a viscosity of 50 to 10,000,000 mPa at 23°C. ⁇ S is a linear organopolysiloxane.
  • R 1 each independently represents an unsubstituted or substituted monovalent hydrocarbon group
  • A each independently represents an alkenyl group
  • m is an integer of 1 to 10,000. It is.
  • the unsubstituted or substituted monovalent hydrocarbon group for R 1 may be linear, branched, or cyclic. Further, the number of carbon atoms is not particularly limited, but preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
  • monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl groups; aralkyl groups such as benzyl and phenethyl groups; chloro Examples include halogenated alkyl groups such as methyl, 3-chloropropyl, and 3,3,3-trifluoropropyl groups, and among these, methyl group is preferred from the viewpoint of heat resistance.
  • the alkenyl group of A may be linear, branched, or cyclic. Further, the number of carbon atoms is not particularly limited, but preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms. Specific examples of the alkenyl group include vinyl, allyl, butenyl, pentenyl, hexenyl and the like, with vinyl being particularly preferred.
  • m is an integer of 1 to 10,000, preferably an integer of 100 to 1,000. If m is 0, it will be highly volatile under atmospheric pressure, and if it exceeds 10,000, it will become highly viscous, resulting in poor workability and will not mix uniformly with components (B) and (C). It becomes difficult.
  • the viscosity of component (i) at 23° C. is 50 to 10,000,000 mPa ⁇ s, preferably 1,000 to 100,000 mPa ⁇ s. If the viscosity is less than 50 mPa ⁇ s, it will easily volatilize under atmospheric pressure or reduced pressure during defoaming, and if it exceeds 10,000,000 mPa ⁇ s, the workability will deteriorate and the components (B) and (C) ) It becomes difficult to mix uniformly with the ingredients. Note that the viscosity in the present invention is a value measured using a rotational viscometer.
  • the molecular weight of component (i) is not particularly limited, but the weight average molecular weight (Mw) is preferably 500 to 500,000, more preferably 1,000 to 100,000.
  • the weight average molecular weight in the present invention is a standard polystyrene equivalent value measured by GPC (gel permeation chromatography) using a THF solvent (the same applies hereinafter).
  • Component (ii) is an organopolysiloxane represented by the following average formula (2).
  • R 1 3 SiO 1/2 p
  • R 1 and A include the same groups as exemplified in formula (1) above, and preferred examples thereof are also the same as above.
  • the ratio (p+q)/r of T units to Q units in component (ii) is preferably 0.3 to 2.0, more preferably 0.5 to 1.0.
  • the weight average molecular weight of component (ii) is preferably 1,000 to 50,000, more preferably 2,000 to 10,000.
  • component (ii) may become solid at 25° C., it may be used after being dissolved in an organopolysiloxane as shown in component (i) above.
  • the usage ratio is preferably ⁇ (i) component ⁇ / ⁇ (ii) component ⁇ (mass ratio) of 0.3 to 10, and 0.5 -3 is more preferable.
  • the viscosity of the mixture of component (i) and component (ii) at 23° C. is preferably 1 to 100,000 mPa ⁇ s, more preferably 5 to 10,000 mPa ⁇ s. If the viscosity is 100,000 mPa ⁇ s or less, fluidity is high and handling is easy.
  • Component (B) in the ultraviolet curable silicone composition of the present invention is represented by the following average formula (3), and preferably contains at least two hydrogen atoms bonded to a silicon atom in one molecule. is a linear organohydrogenpolysiloxane having three elements. (R 1 3 SiO 1/2 ) s (H (3-b) R 1 b SiO 1/2 ) 2-s (HR 1 1 SiO 2/2 ) t (R 1 2 SiO 2/2 ) u (3 )
  • R 1 may be the same as in formula (1) above, but is preferably a methyl group.
  • b is 1 or 2, preferably 2.
  • s is an integer satisfying 0 ⁇ s ⁇ 2, preferably 0 or 2, and more preferably 2.
  • t and u are positive integers satisfying 2 ⁇ t+u ⁇ 800 and 0.6 ⁇ t/(t+u+2) ⁇ 1.0, but 7 ⁇ t+u ⁇ 700 and 0.7 ⁇ u/( A positive integer satisfying t+u+2) ⁇ 0.9 is preferable. If t+u is less than 2, three-dimensional crosslinking cannot be formed and a cured silicone product cannot be obtained. If t+u is more than 800, component (B) becomes highly viscous, and components (A) and (C) ) It becomes difficult to mix with other components. Further, if t/(t+u+2) is less than 0.6, the composition will harden slowly, and if it exceeds 1.0, the hardness of the obtained cured product will change greatly over time.
  • the kinematic viscosity of component (B) at 23° C. is preferably 0.5 to 20,000 mm 2 /s, more preferably 1 to 500 mm 2 /s.
  • the kinematic viscosity is a value measured using a Cannon-Fenske viscometer.
  • the weight average molecular weight of component (B) is preferably 600 to 60,000, more preferably 1,000 to 10,000.
  • the amount of organopolysilixane (B) is preferably 1 to 200 parts by weight, more preferably 1 to 50 parts by weight, per 100 parts by weight of component (A). With such a blending amount, sufficient hardness and strength can be obtained when the ultraviolet curable silicone composition is cured.
  • the organohydrogenpolysiloxane as component (B) has a molar ratio of SiH groups in component (B) to alkenyl groups in component (A) (Si-H/alkenyl group) of 0.8.
  • Si-H/alkenyl group is preferably blended in an amount of 1.0 to 4.0, more preferably 1.7 to 4.0, even more preferably 1.7 to 4.0. It is suitable that the amount is 3.5, more preferably 2.0 to 3.5, particularly preferably 2.0 to 3.0.
  • Component (C) in the ultraviolet curable silicone composition of the present invention is a platinum group metal catalyst that is activated by light with a wavelength of 200 to 500 nm, that is, it is inactive under light shielding, and When irradiated with light with a wavelength of 200 to 500 nm, it changes to a platinum group metal catalyst active at room temperature, and hydrosilylates the alkenyl group in component (A) and the silicon-bonded hydrogen atom in component (B). It is a catalyst to promote reactions.
  • component (C) examples include ( ⁇ 5 -cyclopentadienyl) trialiphatic platinum compounds or derivatives thereof.
  • cyclopentadienyltrimethylplatinum, methylcyclopentadienyltrimethylplatinum, and cyclopentadienyl group-modified derivatives thereof are preferred.
  • a bis( ⁇ -diketonato)platinum compound can also be suitably used as the component (C).
  • bis(acetylacetonato)platinum compounds and derivatives thereof modified with an acetylacetonato group are preferred.
  • the content of component (C) is not particularly limited as long as it promotes curing (hydrosilylation reaction) of the ultraviolet curable silicone composition of the present invention, but the content of component (A) and (B)
  • the amount of metal atoms in component (C) is preferably in the range of 0.01 to 500 ppm, more preferably 0.05 to 100 ppm, and more preferably 0.01 to 100 ppm, based on the total mass of the components. An amount of 50 ppm is even more preferred.
  • components (A) to (C) may be added to the ultraviolet curable silicone composition of the present invention as long as they do not impair the purpose of the present invention.
  • Other components include, for example, reaction control agents that control the reactivity of platinum catalysts, thixotropic control agents such as fumed silica; reinforcing agents such as fumed silica and crystalline silica; metal oxides and metal hydroxides. and viscosity modifiers such as non-reactive silicone oil having no reactive functional groups.
  • the ultraviolet curable silicone composition of the present invention does not contain adhesion aids such as alkoxysilanes and epoxy group-containing compounds, which are commonly used as adhesion agents that impart adhesion to substrates. preferable. These adhesion aid components may stick to the silicon substrate or processing equipment, resulting in contamination and equipment contamination.
  • Light having a wavelength of 200 to 500 nm, preferably 250 to 350 nm is used to cure the ultraviolet curable silicone composition of the present invention.
  • the irradiation intensity is preferably 30 to 2,000 mW/cm 2 and the irradiation dose is preferably 150 to 10,000 mJ/cm 2 .
  • the ultraviolet curable silicone composition of the present invention has excellent productivity because it can be cured at a relatively mild temperature of 100° C. or less after irradiation with ultraviolet rays in a short period of about several minutes. Furthermore, it can be cured in a short time of several minutes to several hours even at room temperature.
  • A-i-1) Organopolysiloxane represented by the following average formula (viscosity 1,000 mPa ⁇ s at 23°C) ViMe 2 SiO (Me 2 SiO) 300 SiMe 2 Vi (A-i-2): Organopolysiloxane represented by the following average formula (viscosity 5,000 mPa ⁇ s at 23°C) ViMe 2 SiO (Me 2 SiO) 430 SiMe 2 Vi (A-ii-1): A mixture of an organopolysiloxane with a weight average molecular weight of 4,500 represented by the average formula below and an organopolysiloxane represented by (A-i-2) above (mass ratio 1: 1) (ViMe 2 SiO 1/2 ) 0.07 (Me 3 SiO 1/2 ) 0.39 (SiO 4/2 ) 0.54
  • (B) Component (B-1): Dimethylsiloxane/methylhydrogensiloxane copolymer (dimethylsiloxane/methylhydrogensiloxane) blocked with trimethylsiloxy groups at both ends of the molecular chain and having a kinematic viscosity of 44.7 mm 2 /s at 23°C, represented by the average formula below. Content of silicon-bonded hydrogen atoms 0.0112 mol/g) (In the formula, the arrangement of each siloxane unit in parentheses is arbitrary.)
  • C Component (C-1): 2-(2-butoxyethoxy)ethyl acetate solution of bisacetylacetonatoplatinum complex (platinum concentration 0.5% by mass)
  • C-2 Toluene solution of methylcyclopentadienyltrimethylplatinum complex (platinum concentration 0.5% by mass)
  • Examples 2-1 to 2-5, Comparative Examples 2-1 to 2-6 The cured products obtained by curing the ultraviolet curable silicone compositions obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-6 were evaluated as follows. The results are shown in Table 2.
  • the ultraviolet curable silicone composition was irradiated with ultraviolet light using a UV-LED lamp with a wavelength of 365 nm at an irradiation intensity of 100 mW/cm 2 and a dose of 3,000 mJ/cm 2 , and then allowed to stand at 23°C for 24 hours.
  • the composition was cured to obtain a cured product.
  • the durometer A hardness of the 6 mm thick cured product was measured using a rubber hardness meter P2-A type (manufactured by Asker).
  • the ultraviolet curable silicone compositions prepared in Examples 1-1 to 1-5 had excellent adhesion to silicon wafers without adding an adhesion aid.
  • the ultraviolet curable silicone compositions of Comparative Examples 1-1 to 1-6 in which components outside the range of component (B) of the present invention were used had poor adhesion to silicon wafers.

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Abstract

A composition containing (A) (i) and/or (ii) (i) polysiloxane (1) AR1 2Si(OR1 2Si)mOSiR1 2A (1) (ii) polysiloxane (2) (R1 3SiO1/2)p(A(3-a)R1 aSiO1/2)q(SiO4/2)r (2) (R1 is a monovalent hydrocarbon group, A is an alkenyl group, m is 1-10,000, p > 0, q > 0, r > 0, p + q + r = 1, a is 1 or 2), (B) hydrogen polysiloxane (3) (R1 3SiO1/2)s(H(3-b)R1 bSiO1/2)2-s(HR1 1SiO2/2)t(R1 2SiO2/2)u (3) (R1 is as above. b is 1 or 2, 0 ≤ s ≤ 2, 2 ≤ t + u ≤ 800, 0.6 ≤ t/(t + u + 2) ≤ 1.0), and (C) a platinum group catalyst activated by light of a wavelength of 200-500 nm, where (B) Si-H groups/(A) alkenyl groups = 0.8-4.0 (molar ratio), adheres well to metal silicon even without adding an adhesion aid.

Description

紫外線硬化型シリコーン組成物、硬化物およびシリコンウェハーコーティング剤UV-curable silicone compositions, cured products and silicone wafer coating agents
　本発明は、紫外線硬化型シリコーン組成物、硬化物およびシリコンウェハーコーティング剤に関する。 The present invention relates to an ultraviolet curable silicone composition, a cured product, and a silicon wafer coating agent.
　シリコーンゴムを得る手法として、白金触媒によるヒドロシリル化反応を用いる硬化手法が広く知られている。紫外線の照射によってヒドロシリル化反応活性を得る、紫外線活性型の白金触媒を使用することで、紫外線硬化型のシリコーン材料へ誘導することができる（特許文献１）。紫外線硬化型のシリコーン材料は、遮光下におけるポットライフが長いうえに、紫外線を照射した後は常温でも速やかに硬化が進む特徴を有するため、例えば大面積の基材上で硬化させる用途において有効である。 As a method for obtaining silicone rubber, a curing method using a hydrosilylation reaction using a platinum catalyst is widely known. By using an ultraviolet-activated platinum catalyst that obtains hydrosilylation reaction activity by irradiation with ultraviolet rays, it is possible to induce an ultraviolet-curable silicone material (Patent Document 1). UV-curable silicone materials have a long pot life under light-shielded conditions, and also have the characteristic of rapidly curing even at room temperature after irradiation with UV rays, so they are effective, for example, in applications where they are cured on large-area substrates. be.
　一方、半導体シリコンの製造においては、シリコン基板に対して数百工程にわたる物理的または化学的な処理を行う加工プロセスが含まれており、処理時にシリコン基板の割れや掘削片による傷といった不良が発生する場合がある。したがって、加工の際にシリコン基板を保護するコーティング剤を用いることで、歩留まりが向上できると考えられる。
　この点、シリコーンゴムは、柔軟性を持ちながら機械的強度に優れているため、シリコン基板の反りや割れを防ぐことができるうえ、耐薬品性にも優れているため、このようなコーティング剤に有用であると考えられる。量産性を向上させるためにシリコン基板が大口径化されている経緯からして、シリコーン材料のなかでも、ポットライフおよび硬化性の速さの観点から、紫外線硬化型のシリコーン材料が有用であると考えられる。 On the other hand, the manufacturing of semiconductor silicon involves hundreds of physical and chemical processing steps on silicon substrates, and defects such as cracks in the silicon substrate and scratches from excavated pieces can occur during processing. There are cases where Therefore, it is thought that the yield can be improved by using a coating agent that protects the silicon substrate during processing.
In this regard, silicone rubber is flexible and has excellent mechanical strength, so it can prevent warping and cracking of the silicon substrate, and it also has excellent chemical resistance, so it is suitable for such coating agents. It is considered useful. Considering the fact that silicon substrates are becoming larger in diameter to improve mass production, UV-curable silicone materials are considered to be useful from the viewpoint of pot life and curing speed. Conceivable.
　しかし、半導体シリコンは、使用する薬品に含まれている不純物によって影響を受けやすいため、例えば洗浄用水やエッチング用ガスには、極めて純度が高いものが使用されている。このためコーティング剤としての利用を考慮する際、シリコーン材料の原料にも特別な注意を払う必要がある。
　シリコーンコーティング剤やシリコーン接着剤には、基材への接着性を付与するためにアルコキシシランやエポキシ基含有化合物等の接着助剤が添加されることが一般的である。しかし、これらの接着助剤成分は、シリコン基板や加工装置内に固着するおそれがあり、コンタミネーションや装置汚染の要因となり得る。 However, semiconductor silicon is easily affected by impurities contained in the chemicals used, so for example, cleaning water and etching gas are used with extremely high purity. Therefore, when considering its use as a coating agent, special attention must be paid to the raw material of the silicone material.
Adhesive aids such as alkoxysilanes and epoxy group-containing compounds are generally added to silicone coating agents and silicone adhesives in order to impart adhesion to substrates. However, these adhesion aid components may stick to the silicon substrate or processing equipment, and may cause contamination and equipment contamination.
特開２０１９－２１８４９５号公報JP2019-218495A
　本発明は、上記事情に鑑みなされたもので、アルコキシシランやエポキシ基含有化合物等の接着助剤を添加しなくても、金属シリコンに対して良好に接着する紫外線硬化型シリコーン組成物を提供することを目的とする。 The present invention was made in view of the above circumstances, and provides an ultraviolet curable silicone composition that adheres well to metal silicon without the addition of an adhesion aid such as an alkoxysilane or an epoxy group-containing compound. The purpose is to
　本発明者らは、上記課題を解決すべく鋭意検討した結果、所定のアルケニル基含有オルガノポリシロキサンと、所定の直鎖状オルガノハイドロジェンポリシロキサンと、波長２００～５００ｎｍの光で活性化される白金族金属触媒とを含む組成物が、接着助剤を添加しなくても金属シリコンに対して良好に接着することを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors discovered that a predetermined alkenyl group-containing organopolysiloxane, a predetermined linear organohydrogenpolysiloxane, and a predetermined linear organohydrogenpolysiloxane that can be activated by light with a wavelength of 200 to 500 nm. The present invention was completed based on the discovery that a composition containing a platinum group metal catalyst adheres well to metallic silicon without the addition of an adhesion aid.
　すなわち、本発明は、
１．　（Ａ）下記（ｉ）および（ｉｉ）のオルガノポリシロキサンの少なくとも一方、
（ｉ）下記式（１）で表され、２３℃における粘度が５０～１０，０００，０００ｍＰａ・ｓである直鎖状オルガノポリシロキサン
　ＡＲ1 2Ｓｉ（ＯＲ1 2Ｓｉ）mＯＳｉＲ1 2Ａ　　（１）
（式中、Ｒ1は、それぞれ独立して、非置換または置換の１価炭化水素基を表し、Ａは、それぞれ独立してアルケニル基を表し、ｍは、１～１０，０００の整数である。）
（ｉｉ）下記平均式（２）で表されるオルガノポリシロキサン
（Ｒ1 3ＳｉＯ1/2）p（Ａ(3-a)Ｒ1 aＳｉＯ1/2）q（ＳｉＯ4/2）r　　（２）
（式中、Ｒ1は、それぞれ独立して、非置換または置換の１価炭化水素基を表し、Ａは、それぞれ独立してアルケニル基を表し、ｐ、ｑおよびｒは、ｐ＞０、ｑ＞０、ｒ＞０、かつ、ｐ＋ｑ＋ｒ＝１を満たす数であり、ａは、１または２である。）
（Ｂ）下記式（３）で表される直鎖状オルガノハイドロジェンポリシロキサン、および
（Ｒ1 3ＳｉＯ1/2）s（Ｈ(3-b)Ｒ1 bＳｉＯ1/2）2-s（ＨＲ1 1ＳｉＯ2/2）t（Ｒ1 2ＳｉＯ2/2）u　（３）
（式中、Ｒ1は、それぞれ独立して、非置換または置換の１価炭化水素基を表し、ｂは、１または２であり、ｓは、０≦ｓ≦２を満たす整数であり、ｔおよびｕは、２≦ｔ＋ｕ≦８００、かつ、０．６≦ｔ／（ｔ＋ｕ＋２）≦１．０を満たす正の整数である。）
（Ｃ）波長２００～５００ｎｍの光で活性化される白金族金属触媒
を含有し、
　前記（Ａ）成分中に含まれるアルケニル基に対する前記（Ｂ）成分中に含まれるＳｉ－Ｈ基のモル比が、Ｓｉ－Ｈ基／アルケニル基＝０．８～４．０であることを特徴とする紫外線硬化型シリコーン組成物、
２．　前記（Ｃ）成分が、（η5－シクロペンタジエニル）三脂肪族白金化合物またはビス（β－ジケトナト）白金化合物を含む１の紫外線硬化型シリコーン組成物、
３．　１または２の紫外線硬化型シリコーン組成物の硬化物、
４．　１または２の紫外線硬化型シリコーン組成物からなるシリコンウェハーコーティング剤
を提供する。 That is, the present invention
1. (A) at least one of the following organopolysiloxanes (i) and (ii),
(i) Linear organopolysiloxane represented by the following formula (1) and having a viscosity of 50 to 10,000,000 mPa·s at 23°C AR 1 2 Si (OR 1 2 Si) m OSiR 1 2 A ( 1)
(In the formula, R 1 each independently represents an unsubstituted or substituted monovalent hydrocarbon group, A each independently represents an alkenyl group, and m is an integer of 1 to 10,000. .)
(ii) Organopolysiloxane (R 1 3 SiO 1/2 ) p (A (3-a) R 1 a SiO 1/2 ) q (SiO 4/2 ) r ( 2)
(In the formula, R 1 each independently represents an unsubstituted or substituted monovalent hydrocarbon group, A each independently represents an alkenyl group, p, q and r are p>0, q >0, r>0, and p+q+r=1, and a is 1 or 2.)
(B) A linear organohydrogenpolysiloxane represented by the following formula (3), and (R 1 3 SiO 1/2 ) s (H (3-b) R 1 b SiO 1/2 ) 2-s (HR 1 1 SiO 2/2 ) t (R 1 2 SiO 2/2 ) u (3)
(In the formula, R 1 each independently represents an unsubstituted or substituted monovalent hydrocarbon group, b is 1 or 2, s is an integer satisfying 0≦s≦2, and t and u is a positive integer satisfying 2≦t+u≦800 and 0.6≦t/(t+u+2)≦1.0.)
(C) contains a platinum group metal catalyst that is activated by light with a wavelength of 200 to 500 nm,
The molar ratio of the Si-H group contained in the component (B) to the alkenyl group contained in the component (A) is Si-H group/alkenyl group = 0.8 to 4.0. an ultraviolet curable silicone composition,
2. 1. The ultraviolet curable silicone composition in which the component (C) contains a (η 5 -cyclopentadienyl) trialiphatic platinum compound or a bis(β-diketonato) platinum compound,
3. A cured product of the ultraviolet curable silicone composition of 1 or 2,
4. A silicon wafer coating agent comprising one or two ultraviolet curable silicone compositions is provided.
　本発明の紫外線硬化型シリコーン組成物は、アルコキシシランやエポキシ基含有化合物等の接着助剤を添加しなくても、金属シリコンに対して良好に接着する。
　また、紫外線を照射する前に十分な作業ゆとり時間が確保でき、紫外線を照射した後は室温でも硬化が速やかに進行するため、シリコンウェハーに対するコーティング剤に適している。 The ultraviolet curable silicone composition of the present invention adheres well to metal silicon even without the addition of an adhesion aid such as an alkoxysilane or an epoxy group-containing compound.
In addition, sufficient working time can be secured before irradiation with ultraviolet rays, and curing proceeds rapidly even at room temperature after irradiation with ultraviolet rays, making it suitable as a coating agent for silicon wafers.
　以下、本発明について具体的に説明する。
　本発明に係る紫外線硬化型シリコーン組成物は、下記（Ａ）～（Ｃ）成分を必須成分として含むものである。 The present invention will be explained in detail below.
The ultraviolet curable silicone composition according to the present invention contains the following components (A) to (C) as essential components.
［１］（Ａ）成分
　本発明の紫外線硬化型シリコーン組成物における（Ａ）成分は、下記（ｉ）成分または（ｉｉ）成分の少なくとも一方を含む。
　（ｉ）成分は、下記式（１）で表され、ケイ素原子に結合したアルケニル基を１分子中に少なくとも２個、好ましくは２個有し、２３℃における粘度が５０～１０，０００，０００ｍＰａ・ｓである直鎖状オルガノポリシロキサンである。
　ＡＲ1 2Ｓｉ（ＯＲ1 2Ｓｉ）mＯＳｉＲ1 2Ａ　　（１） [1] Component (A) Component (A) in the ultraviolet curable silicone composition of the present invention includes at least one of the following components (i) and (ii).
Component (i) is represented by the following formula (1), has at least two, preferably two, alkenyl groups bonded to a silicon atom in one molecule, and has a viscosity of 50 to 10,000,000 mPa at 23°C.・S is a linear organopolysiloxane.
AR 1 2 Si (OR 1 2 Si) m OSiR 1 2 A (1)
　式（１）において、Ｒ1は、それぞれ独立して、非置換または置換の１価炭化水素基を表し、Ａは、それぞれ独立してアルケニル基を表し、ｍは、１～１０，０００の整数である。
　Ｒ1の非置換または置換の１価炭化水素基としては、直鎖、分岐、環状のいずれでもよい。また、その炭素数は特に限定されるものではないが、炭素数１～１０が好ましく、１～５がより好ましい。
　１価炭化水素基の具体例としては、メチル、エチル、ｎ－プロピル、ｎ－ブチル、ｎ－ペンチル、ｎ－ヘキシル、ｎ－ヘプチル基等のアルキル基；ベンジル、フェネチル基等のアラルキル基；クロロメチル、３－クロロプロピル、３，３，３－トリフルオロプロピル基等のハロゲン化アルキル基等が挙げられ、これらの中でも耐熱性の面からメチル基が好ましい。 In formula (1), R 1 each independently represents an unsubstituted or substituted monovalent hydrocarbon group, A each independently represents an alkenyl group, and m is an integer of 1 to 10,000. It is.
The unsubstituted or substituted monovalent hydrocarbon group for R 1 may be linear, branched, or cyclic. Further, the number of carbon atoms is not particularly limited, but preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
Specific examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl groups; aralkyl groups such as benzyl and phenethyl groups; chloro Examples include halogenated alkyl groups such as methyl, 3-chloropropyl, and 3,3,3-trifluoropropyl groups, and among these, methyl group is preferred from the viewpoint of heat resistance.
　Ａのアルケニル基としては、直鎖、分岐、環状のいずれでもよい。また、その炭素数は特に限定されるものではないが、炭素数２～１０が好ましく、２～５がより好ましい。
　アルケニル基の具体例としては、ビニル、アリル、ブテニル、ペンテニル、ヘキセニル基等が挙げられるが、特に、ビニル基が好ましい。
　ｍは、１～１０，０００の整数であるが、１００～１，０００の整数が好ましい。ｍが０であると、大気圧下で揮発性が高くなり、１０，０００を超えると、高粘度となって作業性が悪化するうえに、（Ｂ）成分および（Ｃ）成分と均一に混ざり難くなる。 The alkenyl group of A may be linear, branched, or cyclic. Further, the number of carbon atoms is not particularly limited, but preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms.
Specific examples of the alkenyl group include vinyl, allyl, butenyl, pentenyl, hexenyl and the like, with vinyl being particularly preferred.
m is an integer of 1 to 10,000, preferably an integer of 100 to 1,000. If m is 0, it will be highly volatile under atmospheric pressure, and if it exceeds 10,000, it will become highly viscous, resulting in poor workability and will not mix uniformly with components (B) and (C). It becomes difficult.
　（ｉ）成分の２３℃における粘度は、５０～１０，０００，０００ｍＰａ・ｓであるが、１，０００～１００，０００ｍＰａ・ｓが好ましい。粘度が５０ｍＰａ・ｓ未満であると、大気圧下や、脱泡時の減圧下で揮発し易く、１０，０００，０００ｍＰａ・ｓを超えると、作業性が悪化して（Ｂ）成分および（Ｃ）成分と均一に混ざり難くなる。なお、本発明における粘度は回転粘度計を用いた測定値である。 The viscosity of component (i) at 23° C. is 50 to 10,000,000 mPa·s, preferably 1,000 to 100,000 mPa·s. If the viscosity is less than 50 mPa・s, it will easily volatilize under atmospheric pressure or reduced pressure during defoaming, and if it exceeds 10,000,000 mPa・s, the workability will deteriorate and the components (B) and (C) ) It becomes difficult to mix uniformly with the ingredients. Note that the viscosity in the present invention is a value measured using a rotational viscometer.
　（ｉ）成分の分子量は特に限定されないが、重量平均分子量（Ｍｗ）が５００～５００，０００が好ましく、１，０００～１００，０００がより好ましい。なお、本発明における重量平均分子量は、ＴＨＦ溶媒を用いたＧＰＣ（ゲル浸透クロマトグラフィー）測定による標準ポリスチレン換算値である（以下、同様）。 The molecular weight of component (i) is not particularly limited, but the weight average molecular weight (Mw) is preferably 500 to 500,000, more preferably 1,000 to 100,000. The weight average molecular weight in the present invention is a standard polystyrene equivalent value measured by GPC (gel permeation chromatography) using a THF solvent (the same applies hereinafter).
　（ｉｉ）成分は、下記平均式（２）で表されるオルガノポリシロキサンである。
　（Ｒ1 3ＳｉＯ1/2）p（Ａ(3-a)Ｒ1 aＳｉＯ1/2）q（ＳｉＯ4/2）r　　（２）
　式（２）において、Ｒ1およびＡとしては、上記式（１）で例示した基と同様のものが挙げられ、その好適例も上記と同様である。ｐ、ｑおよびｒは、ｐ＞０、ｑ＞０、ｒ＞０、かつ、ｐ＋ｑ＋ｒ＝１を満たす数であり、ａは、１または２である。 Component (ii) is an organopolysiloxane represented by the following average formula (2).
(R 1 3 SiO 1/2 ) p (A (3-a) R 1 a SiO 1/2 ) q (SiO 4/2 ) r (2)
In formula (2), R 1 and A include the same groups as exemplified in formula (1) above, and preferred examples thereof are also the same as above. p, q, and r are numbers that satisfy p>0, q>0, r>0, and p+q+r=1, and a is 1 or 2.
　（ｉｉ）成分におけるＴ単位とＱ単位との比率（ｐ＋ｑ）／ｒは、０．３～２．０が好ましく、０．５～１．０がより好ましい。
　（ｉｉ）成分の重量平均分子量は１，０００～５０，０００が好ましく、２，０００～１０，０００がより好ましい。
　なお、（ｉｉ）成分は２５℃において固体状となる場合があるため、上記（ｉ）成分で示すようなオルガノポリシロキサンに溶解させて用いてもよい。 The ratio (p+q)/r of T units to Q units in component (ii) is preferably 0.3 to 2.0, more preferably 0.5 to 1.0.
The weight average molecular weight of component (ii) is preferably 1,000 to 50,000, more preferably 2,000 to 10,000.
In addition, since component (ii) may become solid at 25° C., it may be used after being dissolved in an organopolysiloxane as shown in component (i) above.
　（ｉ）成分と（ｉｉ）成分とを併用する場合、それらの使用比率は、｛（ｉ）成分｝／｛（ｉｉ）成分｝（質量比）で０．３～１０が好ましく、０．５～３がより好ましい。
　また、（ｉ）成分と（ｉｉ）成分との混合物の２３℃における粘度は、１～１００，０００ｍＰａ・ｓが好ましく、５～１０，０００ｍＰａ・ｓがより好ましい。粘度が１００，０００ｍＰａ・ｓ以下であれば、流動性が高く、取り扱いが容易である。 When component (i) and component (ii) are used together, their usage ratio is preferably {(i) component}/{(ii) component} (mass ratio) of 0.3 to 10, and 0.5 -3 is more preferable.
Further, the viscosity of the mixture of component (i) and component (ii) at 23° C. is preferably 1 to 100,000 mPa·s, more preferably 5 to 10,000 mPa·s. If the viscosity is 100,000 mPa·s or less, fluidity is high and handling is easy.
［２］（Ｂ）成分
　本発明の紫外線硬化型シリコーン組成物における（Ｂ）成分は、下記平均式（３）で表され、１分子中にケイ素原子に結合した水素原子を少なくとも２個、好ましくは３個有する直鎖状オルガノハイドロジェンポリシロキサンである。
（Ｒ1 3ＳｉＯ1/2）s（Ｈ(3-b)Ｒ1 bＳｉＯ1/2）2-s（ＨＲ1 1ＳｉＯ2/2）t（Ｒ1 2ＳｉＯ2/2）u　（３） [2] Component (B) Component (B) in the ultraviolet curable silicone composition of the present invention is represented by the following average formula (3), and preferably contains at least two hydrogen atoms bonded to a silicon atom in one molecule. is a linear organohydrogenpolysiloxane having three elements.
(R 1 3 SiO 1/2 ) s (H (3-b) R 1 b SiO 1/2 ) 2-s (HR 1 1 SiO 2/2 ) t (R 1 2 SiO 2/2 ) u (3 )
　式（３）において、Ｒ1としては、上記式（１）と同様のものが挙げられるが、メチル基が好ましい。
　ｂは、１または２であるが、２が好ましい。
　ｓは、０≦ｓ≦２を満たす整数であるが、０または２が好ましく、２がより好ましい。
　ｔおよびｕは、２≦ｔ＋ｕ≦８００、かつ、０．６≦ｔ／（ｔ＋ｕ＋２）≦１．０を満たす正の整数であるが、７≦ｔ＋ｕ≦７００、かつ、０．７≦ｕ／（ｔ＋ｕ＋２）≦０．９を満たす正の整数が好ましい。
　ｔ＋ｕが２未満では、三次元架橋を形成することができないため、シリコーン硬化物を得ることができず、８００を超えると、（Ｂ）成分が高粘度となるうえ、（Ａ）成分および（Ｃ）成分との混合が困難となる。また、ｔ／（ｔ＋ｕ＋２）が０．６未満では組成物の硬化が遅く、１．０を超えると得られる硬化物の経時での硬さ変化が大きくなる。 In formula (3), R 1 may be the same as in formula (1) above, but is preferably a methyl group.
b is 1 or 2, preferably 2.
s is an integer satisfying 0≦s≦2, preferably 0 or 2, and more preferably 2.
t and u are positive integers satisfying 2≦t+u≦800 and 0.6≦t/(t+u+2)≦1.0, but 7≦t+u≦700 and 0.7≦u/( A positive integer satisfying t+u+2)≦0.9 is preferable.
If t+u is less than 2, three-dimensional crosslinking cannot be formed and a cured silicone product cannot be obtained. If t+u is more than 800, component (B) becomes highly viscous, and components (A) and (C) ) It becomes difficult to mix with other components. Further, if t/(t+u+2) is less than 0.6, the composition will harden slowly, and if it exceeds 1.0, the hardness of the obtained cured product will change greatly over time.
　（Ｂ）成分の２３℃での動粘度は、０．５～２０，０００ｍｍ2／ｓが好ましく、１～５００ｍｍ2／ｓがより好ましい。ここで、動粘度はキャノン・フェンスケ型粘度計を用いた測定値である。
　（Ｂ）成分の重量平均分子量は、６００～６０，０００が好ましく、１，０００～１０，０００がより好ましい。 The kinematic viscosity of component (B) at 23° C. is preferably 0.5 to 20,000 mm 2 /s, more preferably 1 to 500 mm 2 /s. Here, the kinematic viscosity is a value measured using a Cannon-Fenske viscometer.
The weight average molecular weight of component (B) is preferably 600 to 60,000, more preferably 1,000 to 10,000.
　（Ｂ）成分のオルガノポリシリキサンの配合量は、（Ａ）成分１００質量部に対して１～２００質量部が好ましく、１～５０質量部がより好ましい。このような配合量であれば、紫外線硬化型シリコーン組成物を硬化した際に十分な硬度・強度を得ることができる。
　また、本発明において、（Ｂ）成分のオルガノハイドロジェンポリシロキサンは、（Ａ）成分中のアルケニル基に対する（Ｂ）成分中のＳｉＨ基のモル比（Ｓｉ－Ｈ／アルケニル基）が０．８～４．０となる量で配合されるが、Ｓｉ－Ｈ／アルケニル基が、好ましくは１．０～４．０、より好ましくは１．７～４．０、より一層好ましくは１．７～３．５、さらに好ましくは２．０～３．５、特に好ましくは２．０～３．０となる量で配合されることが好適である。 The amount of organopolysilixane (B) is preferably 1 to 200 parts by weight, more preferably 1 to 50 parts by weight, per 100 parts by weight of component (A). With such a blending amount, sufficient hardness and strength can be obtained when the ultraviolet curable silicone composition is cured.
In addition, in the present invention, the organohydrogenpolysiloxane as component (B) has a molar ratio of SiH groups in component (B) to alkenyl groups in component (A) (Si-H/alkenyl group) of 0.8. Si-H/alkenyl group is preferably blended in an amount of 1.0 to 4.0, more preferably 1.7 to 4.0, even more preferably 1.7 to 4.0. It is suitable that the amount is 3.5, more preferably 2.0 to 3.5, particularly preferably 2.0 to 3.0.
［３］（Ｃ）成分
　本発明の紫外線硬化型シリコーン組成物における（Ｃ）成分は、波長２００～５００ｎｍの光で活性化される白金族金属触媒、すなわち、遮光下で不活性であり、かつ、波長２００～５００ｎｍの光を照射することにより、室温で活性な白金族金属触媒に変化して（Ａ）成分中のアルケニル基と、（Ｂ）成分中のケイ素原子結合水素原子とのヒドロシリル化反応を促進するための触媒である。 [3] Component (C) Component (C) in the ultraviolet curable silicone composition of the present invention is a platinum group metal catalyst that is activated by light with a wavelength of 200 to 500 nm, that is, it is inactive under light shielding, and When irradiated with light with a wavelength of 200 to 500 nm, it changes to a platinum group metal catalyst active at room temperature, and hydrosilylates the alkenyl group in component (A) and the silicon-bonded hydrogen atom in component (B). It is a catalyst to promote reactions.
　このような（Ｃ）成分の具体例としては、（η5－シクロペンタジエニル）三脂肪族白金化合物またはその誘導体が挙げられる。
　中でも、シクロペンタジエニルトリメチル白金、メチルシクロペンタジエニルトリメチル白金、およびそれらのシクロペンタジエニル基が修飾された誘導体が好ましい。
　また、ビス（β－ジケトナト）白金化合物も（Ｃ）成分として好適に用いることができる。
　中でも、ビス（アセチルアセトナト）白金化合物およびそのアセチルアセトナト基が修飾された誘導体が好ましい。 Specific examples of such component (C) include (η 5 -cyclopentadienyl) trialiphatic platinum compounds or derivatives thereof.
Among these, cyclopentadienyltrimethylplatinum, methylcyclopentadienyltrimethylplatinum, and cyclopentadienyl group-modified derivatives thereof are preferred.
Furthermore, a bis(β-diketonato)platinum compound can also be suitably used as the component (C).
Among these, bis(acetylacetonato)platinum compounds and derivatives thereof modified with an acetylacetonato group are preferred.
　（Ｃ）成分の含有量は、本発明の紫外線硬化型シリコーン組成物の硬化（ヒドロシリル化反応）を促進する量であれば特に限定されるものではないが、上記（Ａ）成分と（Ｂ）成分の質量の合計に対して、（Ｃ）成分中の金属原子が質量単位で０．０１～５００ｐｐｍの範囲となる量が好ましく、０．０５～１００ｐｐｍとなる量がより好ましく、０．０１～５０ｐｐｍとなる量がより一層好ましい。 The content of component (C) is not particularly limited as long as it promotes curing (hydrosilylation reaction) of the ultraviolet curable silicone composition of the present invention, but the content of component (A) and (B) The amount of metal atoms in component (C) is preferably in the range of 0.01 to 500 ppm, more preferably 0.05 to 100 ppm, and more preferably 0.01 to 100 ppm, based on the total mass of the components. An amount of 50 ppm is even more preferred.
［４］その他の成分
　本発明の紫外線硬化型シリコーン組成物には、上述した（Ａ）～（Ｃ）成分に加え、本発明の目的を損なわない限り、その他の成分を配合してもよい。
　その他の成分としては、例えば、白金触媒の反応性を制御する反応制御剤、ヒュームドシリカ等のチクソ性制御剤；ヒュームドシリカ、結晶性シリカ等の補強剤；金属酸化物、金属水酸化物等の耐熱向上剤；反応性官能基を有しない非反応性シリコーンオイル等の粘度調整剤などが挙げられる。 [4] Other components In addition to the above-mentioned components (A) to (C), other components may be added to the ultraviolet curable silicone composition of the present invention as long as they do not impair the purpose of the present invention.
Other components include, for example, reaction control agents that control the reactivity of platinum catalysts, thixotropic control agents such as fumed silica; reinforcing agents such as fumed silica and crystalline silica; metal oxides and metal hydroxides. and viscosity modifiers such as non-reactive silicone oil having no reactive functional groups.
　なお、本発明の紫外線硬化型シリコーン組成物は、基材への接着性を付与する接着性付与剤として一般的に用いられる、アルコキシシランやエポキシ基含有化合物等の接着助剤を含まないことが好ましい。これらの接着助剤成分は、シリコン基板や加工装置内に固着するおそれがあり、コンタミネーションや装置汚染が発生する場合がある。 Note that the ultraviolet curable silicone composition of the present invention does not contain adhesion aids such as alkoxysilanes and epoxy group-containing compounds, which are commonly used as adhesion agents that impart adhesion to substrates. preferable. These adhesion aid components may stick to the silicon substrate or processing equipment, resulting in contamination and equipment contamination.
　本発明の紫外線硬化型シリコーン組成物の硬化には、波長２００～５００ｎｍ、好ましくは２５０～３５０ｎｍの光が使用される。硬化速度と変色防止の観点から、照射強度は３０～２，０００ｍＷ／ｃｍ2が好ましく、照射線量は１５０～１０，０００ｍＪ／ｃｍ2が好ましい。 Light having a wavelength of 200 to 500 nm, preferably 250 to 350 nm is used to cure the ultraviolet curable silicone composition of the present invention. From the viewpoint of curing speed and prevention of discoloration, the irradiation intensity is preferably 30 to 2,000 mW/cm 2 and the irradiation dose is preferably 150 to 10,000 mJ/cm 2 .
　本発明の紫外線硬化型シリコーン組成物は、紫外線照射後１００℃以下の比較的温和な温度にて数分程の短時間で硬化させることができるため、生産性に優れている。また、室温においても数分～数時間の短時間で硬化させることができる。 The ultraviolet curable silicone composition of the present invention has excellent productivity because it can be cured at a relatively mild temperature of 100° C. or less after irradiation with ultraviolet rays in a short period of about several minutes. Furthermore, it can be cured in a short time of several minutes to several hours even at room temperature.
　以下、実施例および比較例を挙げて本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
　なお、２３℃における粘度は回転粘度計により、２３℃における動粘度はキャノン・フェンスケ型粘度計により測定した。また、以下において、Ｖｉはビニル基を表し、Ｍｅはメチル基を表す。 EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The viscosity at 23°C was measured using a rotational viscometer, and the kinematic viscosity at 23°C was measured using a Cannon-Fenske viscometer. Further, in the following, Vi represents a vinyl group, and Me represents a methyl group.
［１］紫外線硬化型シリコーン組成物の調製
［実施例１－１～１－５、比較例１－１～１－６］
　下記に示される（Ａ）～（Ｃ）成分を、表１に示す配合量（質量部）にて混合し、紫外線硬化型シリコーン組成物を調製した。 [1] Preparation of ultraviolet curable silicone composition [Examples 1-1 to 1-5, Comparative Examples 1-1 to 1-6]
Components (A) to (C) shown below were mixed in the amounts (parts by mass) shown in Table 1 to prepare an ultraviolet curable silicone composition.
（Ａ）成分
（Ａ－ｉ－１）：下記平均式で表されるオルガノポリシロキサン（２３℃における粘度１，０００ｍＰａ・ｓ）
　ＶｉＭｅ2ＳｉＯ（Ｍｅ2ＳｉＯ）300ＳｉＭｅ2Ｖｉ
（Ａ－ｉ－２）：下記平均式で表されるオルガノポリシロキサン（２３℃における粘度５，０００ｍＰａ・ｓ）
　ＶｉＭｅ2ＳｉＯ（Ｍｅ2ＳｉＯ）430ＳｉＭｅ2Ｖｉ
（Ａ－ｉｉ－１）：下記平均式で表される重量平均分子量４，５００のオルガノポリシロキサンと、上記（Ａ－ｉ－２）で表されるオルガノポリシロキサンとの混合物（質量比１：１）
　（ＶｉＭｅ2ＳｉＯ1/2）0.07（Ｍｅ3ＳｉＯ1/2）0.39（ＳｉＯ4/2）0.54 (A) Component (A-i-1): Organopolysiloxane represented by the following average formula (viscosity 1,000 mPa・s at 23°C)
ViMe 2 SiO (Me 2 SiO) 300 SiMe 2 Vi
(A-i-2): Organopolysiloxane represented by the following average formula (viscosity 5,000 mPa・s at 23°C)
ViMe 2 SiO (Me 2 SiO) 430 SiMe 2 Vi
(A-ii-1): A mixture of an organopolysiloxane with a weight average molecular weight of 4,500 represented by the average formula below and an organopolysiloxane represented by (A-i-2) above (mass ratio 1: 1)
(ViMe 2 SiO 1/2 ) 0.07 (Me 3 SiO 1/2 ) 0.39 (SiO 4/2 ) 0.54
（Ｂ）成分
（Ｂ－１）：下記平均式で表され、２３℃における動粘度が４４．７ｍｍ2／ｓである分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体（ケイ素原子結合水素原子の含有量＝０．０１１２ｍｏｌ／ｇ）
Figure JPOXMLDOC01-appb-C000001
 （式中、括弧が付された各シロキサン単位の配列は任意である。） (B) Component (B-1): Dimethylsiloxane/methylhydrogensiloxane copolymer (dimethylsiloxane/methylhydrogensiloxane) blocked with trimethylsiloxy groups at both ends of the molecular chain and having a kinematic viscosity of 44.7 mm 2 /s at 23°C, represented by the average formula below. Content of silicon-bonded hydrogen atoms = 0.0112 mol/g)
Figure JPOXMLDOC01-appb-C000001
 (In the formula, the arrangement of each siloxane unit in parentheses is arbitrary.)
（Ｂ－２）：下記平均式で表され、２３℃における動粘度が１８．０ｍｍ2／ｓである分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体（ケイ素原子結合水素原子の含有量＝０．００７３ｍｏｌ／ｇ）
Figure JPOXMLDOC01-appb-C000002
 （式中、括弧が付された各シロキサン単位の配列は任意である。） (B- 2 ): Dimethylsiloxane-methylhydrogensiloxane copolymer (silicon-bonded hydrogen Atom content = 0.0073 mol/g)
Figure JPOXMLDOC01-appb-C000002
 (In the formula, the arrangement of each siloxane unit in parentheses is arbitrary.)
（Ｂ－３）：下記平均式で表され、２３℃における動粘度が９９．０ｍｍ2／ｓである分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体（ケイ素原子結合水素原子の含有量＝０．００３７ｍｏｌ／ｇ）
Figure JPOXMLDOC01-appb-C000003
 （式中、括弧が付された各シロキサン単位の配列は任意である。） (B-3): Dimethylsiloxane/methylhydrogensiloxane copolymer (silicon-bonded hydrogen Atom content = 0.0037 mol/g)
Figure JPOXMLDOC01-appb-C000003
 (In the formula, the arrangement of each siloxane unit in parentheses is arbitrary.)
（Ｃ）成分
（Ｃ－１）：ビスアセチルアセトナト白金錯体の酢酸２－（２－ブトキシエトキシ）エチル溶液（白金濃度０．５質量％）
（Ｃ－２）：メチルシクロペンタジエニルトリメチル白金錯体のトルエン溶液（白金濃度０．５質量％） (C) Component (C-1): 2-(2-butoxyethoxy)ethyl acetate solution of bisacetylacetonatoplatinum complex (platinum concentration 0.5% by mass)
(C-2): Toluene solution of methylcyclopentadienyltrimethylplatinum complex (platinum concentration 0.5% by mass)
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
［実施例２－１～２－５、比較例２－１～２－６］
　実施例１－１～１－５および比較例１－１～１－６で得られた紫外線硬化型シリコーン組成物を硬化した硬化物について、下記の評価を行った。結果を表２に示す。 [Examples 2-1 to 2-5, Comparative Examples 2-1 to 2-6]
The cured products obtained by curing the ultraviolet curable silicone compositions obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-6 were evaluated as follows. The results are shown in Table 2.
［硬度］
　紫外線硬化型シリコーン組成物に、波長３６５ｎｍのＵＶ－ＬＥＤランプを用い、照射強度１００ｍＷ／ｃｍ2および線量３，０００ｍＪ／ｃｍ2となるように紫外線を照射後、２３℃で２４時間静置させて組成物を硬化させ、硬化物を得た。６ｍｍ厚みの硬化物のデュロメーターＡ硬度をゴム硬度計Ｐ２－Ａ型（Ａｓｋｅｒ社製）を用いて測定した。 [hardness]
The ultraviolet curable silicone composition was irradiated with ultraviolet light using a UV-LED lamp with a wavelength of 365 nm at an irradiation intensity of 100 mW/cm 2 and a dose of 3,000 mJ/cm 2 , and then allowed to stand at 23°C for 24 hours. The composition was cured to obtain a cured product. The durometer A hardness of the 6 mm thick cured product was measured using a rubber hardness meter P2-A type (manufactured by Asker).
［Ｓｉ接着性］
　シリコンウェハー上に紫外線硬化型シリコーン組成物をスピンコートにより塗布し、波長３６５ｎｍのＵＶ－ＬＥＤランプを用い、照射強度１００ｍＷ／ｃｍ2および線量３，０００ｍＪ／ｃｍ2となるように紫外線を照射後、２３℃で２４時間静置させて組成物を硬化させた。
　上記硬化物層とシリコンウェハーとの界面に沿ってカッターナイフを動かした際、硬化物層がシリコンウェハーから容易に剥がれる場合は「剥離」とし、硬化物層とシリコンウェハーとの界面で剥離しない場合は「接着」として評価した。 [Si adhesion]
An ultraviolet curable silicone composition is applied onto a silicon wafer by spin coating, and then irradiated with ultraviolet light using a UV-LED lamp with a wavelength of 365 nm at an irradiation intensity of 100 mW/cm 2 and a dose of 3,000 mJ/cm 2 . The composition was cured by standing at 23° C. for 24 hours.
When the cutter knife is moved along the interface between the cured material layer and the silicon wafer, if the cured material layer easily peels off from the silicon wafer, it is considered "peeling", and if it does not peel off at the interface between the cured material layer and the silicon wafer. was evaluated as "adhesion".
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表２に示されるように、実施例１－１～１－５で調製した紫外線硬化型シリコーン組成物は、接着助剤を添加することなくシリコンウェハーに対する接着性に優れるものであった。
　一方、本発明の（Ｂ）成分の範囲を外れるものを使用した比較例１－１～１－６の紫外線硬化型シリコーン組成物では、シリコンウェハーに対する接着性に劣るものであることがわかる。 As shown in Table 2, the ultraviolet curable silicone compositions prepared in Examples 1-1 to 1-5 had excellent adhesion to silicon wafers without adding an adhesion aid.
On the other hand, it can be seen that the ultraviolet curable silicone compositions of Comparative Examples 1-1 to 1-6 in which components outside the range of component (B) of the present invention were used had poor adhesion to silicon wafers.

Claims (4)

  1. 　（Ａ）下記（ｉ）および（ｉｉ）のオルガノポリシロキサンの少なくとも一方、
    （ｉ）下記式（１）で表され、２３℃における粘度が５０～１０，０００，０００ｍＰａ・ｓである直鎖状オルガノポリシロキサン
    　ＡＲ1 2Ｓｉ（ＯＲ1 2Ｓｉ）mＯＳｉＲ1 2Ａ　　（１）
    （式中、Ｒ1は、それぞれ独立して、非置換または置換の１価炭化水素基を表し、Ａは、それぞれ独立してアルケニル基を表し、ｍは、１～１０，０００の整数である。）
    （ｉｉ）下記平均式（２）で表されるオルガノポリシロキサン
    （Ｒ1 3ＳｉＯ1/2）p（Ａ(3-a)Ｒ1 aＳｉＯ1/2）q（ＳｉＯ4/2）r　　（２）
    （式中、Ｒ1は、それぞれ独立して、非置換または置換の１価炭化水素基を表し、Ａは、それぞれ独立してアルケニル基を表し、ｐ、ｑおよびｒは、ｐ＞０、ｑ＞０、ｒ＞０、かつ、ｐ＋ｑ＋ｒ＝１を満たす数であり、ａは、１または２である。）
    （Ｂ）下記式（３）で表される直鎖状オルガノハイドロジェンポリシロキサン、および
    （Ｒ1 3ＳｉＯ1/2）s（Ｈ(3-b)Ｒ1 bＳｉＯ1/2）2-s（ＨＲ1 1ＳｉＯ2/2）t（Ｒ1 2ＳｉＯ2/2）u　（３）
    （式中、Ｒ1は、それぞれ独立して、非置換または置換の１価炭化水素基を表し、ｂは、１または２であり、ｓは、０≦ｓ≦２を満たす整数であり、ｔおよびｕは、２≦ｔ＋ｕ≦８００、かつ、０．６≦ｔ／（ｔ＋ｕ＋２）≦１．０を満たす正の整数である。）
    （Ｃ）波長２００～５００ｎｍの光で活性化される白金族金属触媒
    を含有し、
    　前記（Ａ）成分中に含まれるアルケニル基に対する前記（Ｂ）成分中に含まれるＳｉ－Ｈ基のモル比が、Ｓｉ－Ｈ基／アルケニル基＝０．８～４．０であることを特徴とする紫外線硬化型シリコーン組成物。     (A) at least one of the following organopolysiloxanes (i) and (ii),
    (i) Linear organopolysiloxane represented by the following formula (1) and having a viscosity of 50 to 10,000,000 mPa·s at 23°C AR 1 2 Si (OR 1 2 Si) m OSiR 1 2 A ( 1)
    (In the formula, R 1 each independently represents an unsubstituted or substituted monovalent hydrocarbon group, A each independently represents an alkenyl group, and m is an integer of 1 to 10,000. .)
    (ii) Organopolysiloxane (R 1 3 SiO 1/2 ) p (A (3-a) R 1 a SiO 1/2 ) q (SiO 4/2 ) r ( 2)
    (In the formula, R 1 each independently represents an unsubstituted or substituted monovalent hydrocarbon group, A each independently represents an alkenyl group, p, q and r are p>0, q >0, r>0, and p+q+r=1, and a is 1 or 2.)
    (B) A linear organohydrogenpolysiloxane represented by the following formula (3), and (R 1 3 SiO 1/2 ) s (H (3-b) R 1 b SiO 1/2 ) 2-s (HR 1 1 SiO 2/2 ) t (R 1 2 SiO 2/2 ) u (3)
    (In the formula, R 1 each independently represents an unsubstituted or substituted monovalent hydrocarbon group, b is 1 or 2, s is an integer satisfying 0≦s≦2, and t and u is a positive integer satisfying 2≦t+u≦800 and 0.6≦t/(t+u+2)≦1.0.)
    (C) contains a platinum group metal catalyst that is activated by light with a wavelength of 200 to 500 nm,
    The molar ratio of the Si-H group contained in the component (B) to the alkenyl group contained in the component (A) is Si-H group/alkenyl group = 0.8 to 4.0. An ultraviolet curable silicone composition.
  2. 　前記（Ｃ）成分が、（η5－シクロペンタジエニル）三脂肪族白金化合物またはビス（β－ジケトナト）白金化合物を含む請求項１記載の紫外線硬化型シリコーン組成物。 The ultraviolet curable silicone composition according to claim 1, wherein the component (C) contains a (η 5 -cyclopentadienyl) trialiphatic platinum compound or a bis(β-diketonato) platinum compound.
  3. 　請求項１または２記載の紫外線硬化型シリコーン組成物の硬化物。 A cured product of the ultraviolet curable silicone composition according to claim 1 or 2.
  4. 　請求項１または２記載の紫外線硬化型シリコーン組成物からなるシリコンウェハーコーティング剤。 A silicon wafer coating agent comprising the ultraviolet curable silicone composition according to claim 1 or 2.
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JP2013063391A (en) * 2011-09-16 2013-04-11 Shin-Etsu Chemical Co Ltd Method of forming cured thin film using photocurable silicone resin composition
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