WO2023038488A1 - Composition for forming film, and film formed therefrom - Google Patents

Composition for forming film, and film formed therefrom Download PDF

Info

Publication number
WO2023038488A1
WO2023038488A1 PCT/KR2022/013594 KR2022013594W WO2023038488A1 WO 2023038488 A1 WO2023038488 A1 WO 2023038488A1 KR 2022013594 W KR2022013594 W KR 2022013594W WO 2023038488 A1 WO2023038488 A1 WO 2023038488A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
composition
forming
independently
formula
Prior art date
Application number
PCT/KR2022/013594
Other languages
French (fr)
Korean (ko)
Inventor
유선
오현주
Original Assignee
주식회사 헤라켐테크놀러지
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 헤라켐테크놀러지 filed Critical 주식회사 헤라켐테크놀러지
Publication of WO2023038488A1 publication Critical patent/WO2023038488A1/en

Links

Classifications

    • 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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements

Definitions

  • the present invention relates to a composition for film formation and a film formed therefrom, and more particularly, to a composition for film formation comprising a siloxane resin having a specific structure and a film formed therefrom.
  • Optical components, electronic components, flat panel display panels, etc. are immersed in a solvent, acid or alkali solution during the manufacturing process, and when forming a wiring electrode layer by sputtering, the device surface is locally exposed to high temperatures. . Therefore, in order to prevent deterioration or damage to the element by these treatments, it is performed to provide a protective film comprising a thin film resistant to these treatments on the surface of the element.
  • a protective film has been used to protect and insulate a TFT (Thin Film Transistor) circuit.
  • an inorganic protective film such as silicon nitride has been used as such a protective film, but there is a problem in that it is difficult to improve an aperture ratio due to a high dielectric constant value. To overcome this problem, demand for an organic insulating film having a low dielectric constant is increasing.
  • an insulating film of such a liquid crystal display device it must have excellent insulation properties, low thermal expansion to reduce stress at the interface when coated on a substrate, and must also have physically strong characteristics.
  • a film-forming composition for forming an insulating film, a transparent protective film, and the like requires various physical properties depending on the intended use.
  • the present invention has been made to solve the problems described above, and the present invention provides a composition for forming a film for forming a protective film or an insulating film applied to an optical component, a display panel, and the like, and a film formed therefrom.
  • the present invention provides a film-forming composition for forming a film that is transparent, has high heat resistance and light resistance, and has excellent water resistance, and a film formed therefrom.
  • thermal acid generators or thermal base generators thermal acid generators or thermal base generators
  • a siloxane resin including repeating units represented by Formulas 1 and 2 below.
  • R 1 to R 4 are each independently hydrogen, (C1-C10)alkyl or (C1-C10)alkoxy;
  • R 11 and R 12 are each independently (C1-C10)alkyl
  • R 13 and R 14 are each independently (C6-C12)aryl
  • p and q are independently of each other an integer from 2 to 10;
  • s and t are 0.5 ⁇ s ⁇ 1.0 in molar ratio; t is 0 ⁇ t ⁇ 0.5.
  • the thermal acid generator is Bis (4-t-butylphenyliodonium) trifluoromethanesulfonate, triarylsulfonium hexafluoroandimonate, triarylsulfone one or two or more selected from um hexafluorophosphate, tetramethylammonium trifluoromethanesulfonate, and triethylamnefluorosulfate;
  • the thermal base generator is tetramethylammonium acetate, tetramethylammonium octylate, tetrabutylammonium acetate, tetrabutylammonium octylate, trimethylbenzylammonium acetate, azabicycloundeceneformate, triethylamine p-toluenesulfonate It may be one or two or more selected from among.
  • the thermal acid generator or thermal base generator according to an embodiment of the present invention may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the siloxane resin.
  • the siloxane resin according to an embodiment of the present invention may have a weight average molecular weight of 5000 to 100,000 g/mol.
  • R 1 to R 4 in Formulas 1 and 2 are hydrogen or (C1-C4)alkyl;
  • R 11 and R 12 are each independently (C1-C4)alkyl,
  • R 13 and R 14 are independently of each other or (C6-C10)aryl;
  • p and q may be each independently an integer of 2 to 5.
  • the film-forming composition according to an embodiment of the present invention may further include (meth)acrylic acid ester, and specifically, (meth)acrylic acid ester is (meth)acrylic acid ester of dihydric or higher alcohol or functional groups of 2 or more ( It may be a steroligomer in meth)acrylic acid.
  • (meth)acrylic acid ester is (meth)acrylic acid ester of dihydric or higher alcohol or functional groups of 2 or more ( It may be a steroligomer in meth)acrylic acid.
  • the film-forming composition according to an embodiment of the present invention may further include an optical radical generator or a thermal radical generator.
  • the composition for forming a film according to an embodiment of the present invention may be used for forming a protective film or an insulating film for an electronic device.
  • the present invention provides a film made of the film-forming composition according to an embodiment of the present invention.
  • the film-forming composition according to an embodiment of the present invention contains a siloxane resin containing a specific janten skeleton, so it has better heat resistance and resistance, so that deterioration such as coloration does not occur even after long-term use, and it has solvent resistance, acid resistance, It has surprisingly good alkalinity and water resistance.
  • composition for film formation according to an embodiment of the present invention uses a thermal acid generator or a thermal base generator, the thermal acid generator or thermal base generator does not remain in the film even after the film is formed, and the physical properties of the film produced therefrom are deteriorated. has the advantage of not causing
  • the film formed from the film-forming composition according to an embodiment of the present invention has excellent physical properties as a protective film or an insulating film for electronic devices.
  • the present invention provides a film-forming composition having improved heat resistance and durability by including a siloxane resin having a specific structure of the janten skeleton and a siloxane structure, the film-forming composition of the present invention,
  • thermal acid generators or thermal base generators thermal acid generators or thermal base generators
  • a siloxane resin including repeating units represented by Formulas 1 and 2 below.
  • R 1 to R 4 are each independently hydrogen, (C1-C10)alkyl or (C1-C10)alkoxy;
  • R 11 and R 12 are each independently (C1-C10)alkyl
  • R 13 and R 14 are each independently (C6-C12)aryl
  • p and q are independently of each other an integer from 2 to 10;
  • s and t are 0.5 ⁇ s ⁇ 1.0 in molar ratio; t is 0 ⁇ t ⁇ 0.5.
  • the film-forming composition of the present invention includes a siloxane resin containing a structural unit containing a janten skeleton, which is a specific structure, so that a film with improved heat resistance and durability can be formed while maintaining transparency. there is.
  • R 1 to R 4 in Formulas 1 and 2 are hydrogen or (C1-C4)alkyl;
  • R 11 and R 12 are each independently (C1-C4)alkyl,
  • R 13 and R 14 are independently (C6-C10)aryl;
  • p and q may be each independently an integer of 2 to 5, more preferably R 1 to R 4 are hydrogen or (C1-C3)alkyl;
  • R 11 and R 12 may each independently be (C1-C3)alkyl,
  • R 13 and R 14 may each independently be phenyl, biphenyl, 1-naphthyl or 2-naphthyl, and
  • p and q may be 2 It may be an integer from 4 to 4.
  • s and t are preferably 0.6 ⁇ s ⁇ 0.9 in Formulas 1 and 2 of the present invention; It may be 0.1 ⁇ t ⁇ 0.4, more preferably 0.7 ⁇ s ⁇ 0.9; 0.1 ⁇ t ⁇ 0.2, more preferably 0.8 ⁇ s ⁇ 0.9; It may be 0.1 ⁇ t ⁇ 0.2.
  • R 11 and R 12 are each independently methyl, ethyl or n-propyl, and R 13 and R 14 may be phenyl.
  • the siloxane resin according to an embodiment of the present invention may have a weight average molecular weight of 5000 to 200,000 g/mol, preferably 10,000 to 100,000 g/mol, and more preferably 20,000 to 100,000 g/mol.
  • the siloxane resin according to an embodiment of the present invention is a hydroxylation polymerization reaction of a monomer that may have a repeating unit of Formula 1 and hydrosiloxanes, which are monomers that may have a repeating unit of Formula 2, in the presence of a catalyst can be manufactured with
  • the siloxane resin according to an embodiment of the present invention may be prepared by polymerizing a monomer that may have a repeating unit of Chemical Formula 1 and a monomer that may have a repeating unit of Chemical Formula 2 above.
  • it may be prepared by polymerizing a unit of Formula 1-1 and a unit of Formula 2-1 below.
  • R 1 to R 4 , R 11 to R 14 , s and t are the same as defined in Formulas 1 and 2, and p and q are integers from 0 to 8.
  • siloxane resin prepared according to one embodiment of the present invention may be represented by Formula 3 below.
  • R 1 to R 4 , R 11 to R 14 , p, q, s and t are the same as defined in Formulas 1 and 2.
  • the siloxane resin according to an embodiment of the present invention includes both alternating copolymers and random copolymers.
  • the siloxane resin of the present invention can be prepared in the presence of a catalyst, and the catalyst used in this case is not limited, but examples thereof include platinum group metals such as platinum (including platinum black), rhodium, and palladium; H 2 PtCl 4 nH 2 O, H 2 PtCl 6 nH 2 O, NaHPtCl 6 nH 2 O, KHPtCl 6 nH 2 O, Na 2 PtCl 6 nH 2 O, K 2 PtCl 4 nH 2 O, PtCl 4 nH 2 O, PtCl 2 , Na 2 HPtCl 4 nH 2 O (in the formula, n is preferably an integer of 0 to 6, particularly preferably 0 or 6) Platinum chloride, chloroplatinic acid and chloride platinate; rhodium-olefin complex; Chlorotris(triphenylphosphine)rhodium (so-called Wilkinson's catalyst); Platinum chloride, chlor
  • an organic solvent may be used if necessary.
  • the organic solvent for example, hydrocarbon-based organic solvents such as toluene and xylene are preferable.
  • the polymerization temperature is, for example, 40 to 150°C, particularly preferably 80 to 120°C. If the polymerization temperature is too low, it may take a long time to complete polymerization, and if the polymerization temperature is too high, the catalyst may not be activated.
  • the polymerization time depends on the type and amount of the polymer, but is preferably completed within about 0.5 to 10 hours, particularly within 0.5 to 5 hours, in order to prevent moisture from entering the polymerization system.
  • organic hydrosiloxanes tend to cause disproportionation reactions as side reactions, and since hydroxylation polymerization reactions are generally exothermic reactions, it is preferable to add the organic hydrosiloxanes dropwise.
  • the siloxane resin of the present invention has a specific structure of janten, and at the same time, by adjusting the content of substituents of hydroxyloxanes, it has more excellent resistance, water resistance, acid resistance and alkali resistance.
  • the siloxane resin of the present invention is very useful for forming a protective film or an insulating film.
  • the siloxane resin of the present invention may be 30 to 70% by weight, preferably 35 to 65% by weight, more preferably 40 to 60% by weight based on the total weight of the siloxane resin composition.
  • the thermal acid generator and the thermal base generator according to an embodiment of the present invention can be used as long as they are used in the technical field of the present invention, but in terms of a preferred combination with the siloxane resin of the present invention, the thermal acid generator is Bis (4 -t-butylphenyliodonium)trifluoromethanesulfonate (Bis (4-tbutylphenyl iodonium) trifluoromethanesulfonate), triarylsulfoniumhexafluoroantimonate, triarylsulfonium hexafluoro one or two or more selected from triarylsulfoniumhexafluorophosphate, tetramethylammoniumtrifluoromethanesulfonate, and triethylamnefluorosulfate;
  • the thermal base generator is tetramethylammoniumacetate, tetramethylammoniumoctylate, tetrabutylammoniumacetate, tetrabutylammoniumoctylate, trimethylbenzylammoniumacetate, azabicyclo It may be one or two or more selected from undeceneformate (Azabicycloundeceneformate) and triethylamine p-toluenesulfonate.
  • the thermal acid generator or thermal base generator according to an embodiment of the present invention may be used in an amount of 0.01 to 10 parts by weight, specifically 0.05 to 10 parts by weight, and more specifically 0.1 to 8 parts by weight, based on 100 parts by weight of the siloxane resin.
  • the thermal acid generator according to an embodiment of the present invention generates a strong acid and a strong base in a temperature range of 50 to 250 °C. Therefore, the thermal acid generator or thermal base generator according to an embodiment of the present invention generates a strong acid volatilized in the range of 20 to 250 ° C as the siloxane resin according to an embodiment of the present invention is heated at a temperature of 50 ° C or higher. It may be a thermal acid generator to generate a strong base volatilized in the range of 20 ⁇ 250 °C, or a thermal base generator.
  • the film-forming composition according to an embodiment of the present invention may further include (meth)acrylic acid ester.
  • (meth)acrylic acid ester By adding (meth)acrylic acid ester to the composition for forming a film according to an embodiment of the present invention, transparency of the formed film can be maintained to the maximum and thermosetting properties of the composition for film formation can be imparted. Furthermore, flexibility, hardness and toughness of the formed film can be controlled according to the type of (meth)acrylic acid ester added, and the refractive index or flame resistance of the film can be controlled.
  • a specific example of the (meth)acrylic acid ester according to an embodiment of the present invention is methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate ), Butyl methacrylate, Butyl acrylate, 2-ethylhexyl acrylate, Hydroxyethyl acrylate, Benzyl acrylate, Phenoxyethyl acrylate, tetrahydrofurfulyl acrylate, phenyl acrylate, naphthyl acrylate, phenanthryl acrylate, etc.
  • the film-forming composition according to an embodiment of the present invention may further include an optical radical generator or a thermal radical generator.
  • an optical radical generator or a thermal radical generator By including an optical radical generator or a thermal radical generator, curing can be accelerated by radicals.
  • Examples of the photoradical generator according to an embodiment of the present invention include tert-butylperoxy-iso-butylate, 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [ ⁇ -(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butylperoxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexenehydroperoxide, ⁇ -(iso-propylphenyl)-iso-propylhydroperoxide, tert-butylhydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4 -bis(tert-butyldioxy)valerate, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-buty
  • Photoradical generators can be obtained as commercial products, for example, IRGACURE (registered trademark) 651, IRGACURE 184, IRGACURE 500, IRGACURE 2959, IRGACURE 127, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE 379EG , IRGACURE 819, IRGACURE 819DW, IRGACURE 1800, IRGACURE 1870, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250, IRGACURE 1173, IRGACURE MBF, IRGACURE TPO, VICURE-10, VICURE-55 (above, manufactured by STDAUFFER Co.) , ESACURE KIP150, ESACURE TZT, ESACURE 1001, ESACURE KTO46, ESACURE KB1, ESACURE KL200, ESACURE KS300, ESACURE EB
  • thermal radical generating agent examples include oligomers having a molecular weight of 3,000 to 100,000, such as epoxy acrylate oligomer, urethane acrylate oligomer, polyester acrylate oligomer, silicone acrylate oligomer, and novolak resin acrylate.
  • the film-forming composition according to an embodiment of the present invention may further include additional additives, and the additional additives may include solvents, other organic resins, crosslinking agents, solvents, silica, surfactants, dyes, viscosity modifiers, and antifoaming agents.
  • the solvent may be alcohols such as ethanol or 2-propanol, or ketones such as methyl ethyl ketone or acetone.
  • the organic resin may be a solvent-soluble alkyd resin, an acrylic resin, an epoxy resin, or a urethane resin.
  • the crosslinking agent a polyacrylate monomer or isocyanuric acid crosslinked with acrylic may be used.
  • the film-forming composition of the present invention may further include an organic solvent, and any organic solvent that can be used within the range recognized by those skilled in the art is possible, but for example, methanol, ethanol, 1-propanol, 2- Propanol, 1-butanol, 2-butanol, sec-butane, 1-pentanol, 2-methylbutanol, 3-methylbutanol, 2-pentanol, 4-methyl-2-pentanol, cyclohexanol, methylcyclohexa alcohols such as nol, n-hexanol, furfuryl alcohol, furfuryl methanol, tetrahydrofurfuryl alcohol, and benzyl alcohol; Acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, methyl t-butyl ketone, methyl n-pentyl ketone, methyl n-hexyl ket
  • glycol monoethers diethylene glycol diethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; diethylene glycol acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monon-butyl ether acetate; dipropylene glycol monoethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether; dipropylene glycol diethers such as dipropylene glycol dimethyl ether; Dipropylene glycol, such as dipropylene glycol monomethyl ether, triethylene glycol monoethyl ether, trisilene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, tripropylene glycol monomethyl
  • any one or two or more selected from ethanol, 2-propanol and secbutyl alcohol, and any one or more selected from propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, and n-propyl acetate It may be a mixture of two or more.
  • an example for preparing a composition for forming a film according to an embodiment of the present invention is as follows. However, since this is only one embodiment of the present invention, the present invention is not limited thereto.
  • the product did not have absorption peaks derived from a hydroxy group and an allyl group, and that the hydroxylation reaction was completed. Moreover, it had an absorption peak derived from a siloxane bond at 1050 cm -1 . Further, as a result of measuring the molecular weight by GPC, the weight average molecular weight was 26,000 g/mol in terms of polystyrene.
  • siloxane resin prepared in Example 1 and 3 parts by weight of tetramethylammonium based on 100 parts by weight of the siloxane resin were added to 1 liter of butyl acetate, mixed with sufficient stirring, and aged at 0 ° C. for 12 hours to obtain a film-forming composition manufactured.
  • a film was formed in the same manner as in Example 2, except that bis(4-t-butylphenyliodonium)trifluoromethanesulfonate was used instead of tetramethylammonium.
  • a film was formed in the same manner as in Example 2, except that 1 part by weight of dipentaerythritol hexaacrylate was added to 100 parts by weight of the siloxane resin in Example 2.
  • Example 2 the film was formed in the same manner as in Example 2, except that 1 part by weight of dipentaerythritol hexaacrylate and 0.01 part by weight of IRGACURE 184 as a photonic polycalcium generator were added with respect to 100 parts by weight of the siloxane resin. formed.
  • a film was formed in the same manner as in Example 2, except that 3 parts by weight of tetramethylammonium was not used in Example 2.
  • the film cured with the film-forming composition of the present invention comprising a combination of a specific siloxane resin composition and a thermal acid generator or a thermal base generator has high pencil hardness and chemical resistance.
  • the pencil hardness of the film prepared from the film-forming composition of Examples 2 to 5 of the present invention is more improved compared to the film prepared from the film-forming composition of Comparative Example 1 that does not contain a thermal acid generator or a thermal base generator. And it can be seen that it has chemical resistance.
  • the film made of the film-forming composition of Example 2 of the present invention containing a thermal acid generator has improved physical properties. Able to know.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silicon Polymers (AREA)

Abstract

The present invention relates to a composition for forming a film, and to a film formed therefrom. The composition for forming a film of the present invention comprises a thermal acid generator or a thermal base generator, and a siloxane resin including a specific structure, and thus, it is possible to manufacture a film having further improved physical properties.

Description

피막형성용 조성물 및 이로부터 형성된 피막Composition for film formation and film formed therefrom
본 발명은 피막형성용 조성물 및 이로부터 형성된 피막에 관한 것으로, 상세하게는 특정한 구조를 포함하는 실록산 수지를 포함하는 피막형성용 조성물 및 이로부터 형성된 피막에 관한 것이다.The present invention relates to a composition for film formation and a film formed therefrom, and more particularly, to a composition for film formation comprising a siloxane resin having a specific structure and a film formed therefrom.
광학부품, 전자기 부품, 평판 디스플레이 패널 등은 그 제조 공정 중에 용제, 산 또는 알칼리 용액 등에 의한 표시 소자의 침지 처리가 행해지며, 스퍼터링에 의해 배선 전극층을 형성할 때에는 소자 표면이 국부적으로 고온에 노출된다. 따라서, 이러한 처리에 의해서 소자가 열화 또는 손상되는 것을 방지하기 위해, 이들 처리에 대하여 내성을 갖는 박막을 포함하는 보호막을 소자의 표면에 설치하는 것이 행해지고 있다.Optical components, electronic components, flat panel display panels, etc., are immersed in a solvent, acid or alkali solution during the manufacturing process, and when forming a wiring electrode layer by sputtering, the device surface is locally exposed to high temperatures. . Therefore, in order to prevent deterioration or damage to the element by these treatments, it is performed to provide a protective film comprising a thin film resistant to these treatments on the surface of the element.
즉, 광학부품, 디스플레이 패널의 표면 긁힘 현상 등 기계적 외상으로부터 보호하고자 하거나, 내화학성 등을 지니도록 하는 것을 목적으로 하는 한편, 기기의 사용시 방출되는 전자파로부터 인체를 보호하고자 보호막을 형성한다.That is, to protect against mechanical trauma such as surface scratches of optical components and display panels, or to have chemical resistance, etc., while forming a protective film to protect the human body from electromagnetic waves emitted during use of the device.
또한 박막 트랜지스터(TFT)형 액정표시장치 등의 디스플레이 장치에 있어서, TFT(Thin Film Transistor)회로를 보호하고, 절연시키기 위한 용도로 보호막이 사용되어 왔다.Also, in a display device such as a thin film transistor (TFT) type liquid crystal display device, a protective film has been used to protect and insulate a TFT (Thin Film Transistor) circuit.
통상적으로 이러한 보호막은 실리콘 나이트라이드 등의 무기계 보호막이 이용되어 왔으만, 유전 상수값이 높아서 개구율을 향상시키기 어려운 문제점이 있어서, 이를 극복하기 위하여 유전율이 낮은 유기절연막에 대한 수요가 증가하고 있다.In general, an inorganic protective film such as silicon nitride has been used as such a protective film, but there is a problem in that it is difficult to improve an aperture ratio due to a high dielectric constant value. To overcome this problem, demand for an organic insulating film having a low dielectric constant is increasing.
이러한 액정표시장치의 절연막으로서 절연성이 우수하여야 함은 물론, 기판 위에 코팅되었을 때 계면에서의 응력을 줄이기 위하여 낮은 열팽창성을 가져야 하며, 또한 물리적으로 강인한 특성을 지녀야 한다.As an insulating film of such a liquid crystal display device, it must have excellent insulation properties, low thermal expansion to reduce stress at the interface when coated on a substrate, and must also have physically strong characteristics.
따라서 절연막, 투명 보호막 등을 형성하기위한 피막형성용 조성물은 목적하는 용도에 따라 다양한 물성이 요구된다.Therefore, a film-forming composition for forming an insulating film, a transparent protective film, and the like requires various physical properties depending on the intended use.
그러나 일반적으로 투명성을 가져야하며, 내열성 및 내광성이 높고 장기간에 걸쳐 착색, 황변, 백화 등의 변질을 일으키지 않으며, 내용제성, 내산성, 내알칼리성 및 내수성이 우수해야한다.However, in general, it must have transparency, have high heat resistance and light resistance, do not cause deterioration such as discoloration, yellowing, and whitening over a long period of time, and must have excellent solvent resistance, acid resistance, alkali resistance, and water resistance.
이에 다양한 절연막 또는 보호막을 형성하기위한 조성물이 연구되고 있으나, 여전히 향상된 물성을 가지는 피막형성용 조성물이 필요한 실정이다.Accordingly, a composition for forming a variety of insulating films or protective films has been studied, but there is still a need for a film-forming composition having improved physical properties.
본 발명은 전술한 바와 같은 문제점을 해결하기 위하여 안출된 것으로서, 본 발명은 광학부품, 디스플레이용 패널 등에 적용되는 보호막 또는 절연막을 형성하기위한 피막형성용 조성물 및 이로부터 형성된 피막을 제공한다.The present invention has been made to solve the problems described above, and the present invention provides a composition for forming a film for forming a protective film or an insulating film applied to an optical component, a display panel, and the like, and a film formed therefrom.
본 발명은 투명성하며, 내열성 및 내광성이 높고 내수성이 우수한 피막을 형성하기위한 피막형성용 조성물 및 이로부터 형성된 피막을 제공하는 것으로, 본 발명의 피막형성용 조성물은 The present invention provides a film-forming composition for forming a film that is transparent, has high heat resistance and light resistance, and has excellent water resistance, and a film formed therefrom.
열산 발생제 또는 열염기 발생제; 및thermal acid generators or thermal base generators; and
하기 화학식 1 및 화학식 2로 표시되는 반복단위를 포함하는 실록산 수지;를 포함한다. A siloxane resin including repeating units represented by Formulas 1 and 2 below.
[화학식 1] [Formula 1]
Figure PCTKR2022013594-appb-img-000001
Figure PCTKR2022013594-appb-img-000001
[화학식 2][Formula 2]
Figure PCTKR2022013594-appb-img-000002
Figure PCTKR2022013594-appb-img-000002
상기 화학식 1 및 화학식 2에서,In Formula 1 and Formula 2,
R1 내지 R4는 서로 독립적으로 수소, (C1-C10)알킬 또는 (C1-C10)알콕시이며;R 1 to R 4 are each independently hydrogen, (C1-C10)alkyl or (C1-C10)alkoxy;
R11 및 R12는 서로 독립적으로 (C1-C10)알킬이며,R 11 and R 12 are each independently (C1-C10)alkyl;
R13 및 R14는 서로 독립적으로 (C6-C12)아릴이며;R 13 and R 14 are each independently (C6-C12)aryl;
p 및 q는 서로 독립적으로 2 내지 10의 정수이며;p and q are independently of each other an integer from 2 to 10;
s 및 t는 몰비로 0.5 ≤ s ≤1.0이며; t는 0 ≤ t ≤ 0.5이다.s and t are 0.5 ≤ s ≤ 1.0 in molar ratio; t is 0 ≤ t ≤ 0.5.
구체적으로 본 발명의 일 실시예에 따른 열산 발생제는 Bis(4-t-부틸페닐이오도니움)트리플루오로메타네술포네이트, 트리아릴술포니움헥사플루오로 안디모네이트, 트리아릴술포니움헥사플로오로포스페이트, 테트라메틸암모늄트리플루오로메타네술포네이트, 트리 에틸암네플루오로설페이트 중에서 선택되는 하나 또는 둘 이상이며; 열염기 발생제는 테트라메틸암모늄아세테이트, 테트라메틸암모늄옥틸레이트, 테트라부틸암모늄아세테이트, 테트라부틸암모늄옥틸레이트, 트리메틸벤질암모늄아세테이트, 아자비시클로운데센포르메이트 (Azabicycloundeceneformate), 트리에틸아민p-톨루엔술포네이트 중에서 선택되는 하나 또는 둘 이상일 수 있다.Specifically, the thermal acid generator according to an embodiment of the present invention is Bis (4-t-butylphenyliodonium) trifluoromethanesulfonate, triarylsulfonium hexafluoroandimonate, triarylsulfone one or two or more selected from um hexafluorophosphate, tetramethylammonium trifluoromethanesulfonate, and triethylamnefluorosulfate; The thermal base generator is tetramethylammonium acetate, tetramethylammonium octylate, tetrabutylammonium acetate, tetrabutylammonium octylate, trimethylbenzylammonium acetate, azabicycloundeceneformate, triethylamine p-toluenesulfonate It may be one or two or more selected from among.
본 발명의 일 실시예에 따른 열산 발생제 또는 열염기 발생제는 실록산 수지 100중량부에 대하여 0.01 ~ 10중량부 포함될 수 있다.The thermal acid generator or thermal base generator according to an embodiment of the present invention may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the siloxane resin.
구체적으로 본 발명의 일 실시예에 따른 실록산 수지는 중량평균분자량이 5000 내지 100,000g/mol일 수 있다.Specifically, the siloxane resin according to an embodiment of the present invention may have a weight average molecular weight of 5000 to 100,000 g/mol.
바람직하게 본 발명의 일 실시예에 따른 화학식 1 및 2에서 R1 내지 R4는 수소 또는 (C1-C4)알킬이며; R11 및 R12는 서로 독립적으로 (C1-C4)알킬이며, R13 및 R14는 서로 독립적으로 또는 (C6-C10)아릴이며; p 및 q는 서로 독립적으로 2 내지 5의 정수일 수 있다.Preferably, R 1 to R 4 in Formulas 1 and 2 according to an embodiment of the present invention are hydrogen or (C1-C4)alkyl; R 11 and R 12 are each independently (C1-C4)alkyl, R 13 and R 14 are independently of each other or (C6-C10)aryl; p and q may be each independently an integer of 2 to 5.
바람직하게 본 발명의 일 실시예에 따른 피막형성용 조성물은 (메타)아크릴산에스테르가 더 포함될 수 있으며, 구체적으로 (메타)아크릴산에스테르는 2가 이상 알코올의 (메타)아크릴산에스테르 또는 관능기수 2이상의 (메타)아크릴산에 스테르올리고머일 수 있다.Preferably, the film-forming composition according to an embodiment of the present invention may further include (meth)acrylic acid ester, and specifically, (meth)acrylic acid ester is (meth)acrylic acid ester of dihydric or higher alcohol or functional groups of 2 or more ( It may be a steroligomer in meth)acrylic acid.
본 발명의 일 실시예에 따른 피막형성용 조성물은 광라디칼발생제 또는 열라디칼발생제를 더 포함할 수 있다.The film-forming composition according to an embodiment of the present invention may further include an optical radical generator or a thermal radical generator.
바람직하게 본 발명의 일 실시예에 따른 피막형성용 조성물은 전자소자의 보호막형성용 또는 절연막형성용일 수 있다.Preferably, the composition for forming a film according to an embodiment of the present invention may be used for forming a protective film or an insulating film for an electronic device.
또한 본 발명은 본 발명의 일 실시예에 따른 피막형성용 조성물로 제조된 피막을 제공한다.In addition, the present invention provides a film made of the film-forming composition according to an embodiment of the present invention.
본 발명의 일 실시예에 따른 피막형성용 조성물은 특정한 쟌텐골격을 포함하는 실록산 수지를 포함함으로써 보다 우수한 내열성 및 내성을 가져 장기간의 사용에도 착색 등의 변질이 발생되지 않으며, 내용제성, 내산성, 내알칼리성 및 내수성이 놀랍도록 우수하다.The film-forming composition according to an embodiment of the present invention contains a siloxane resin containing a specific janten skeleton, so it has better heat resistance and resistance, so that deterioration such as coloration does not occur even after long-term use, and it has solvent resistance, acid resistance, It has surprisingly good alkalinity and water resistance.
또한 본 발명의 일 실시예에 따른 피막형성용 조성물은 열산 발생제 또는 열염기 발생제를 사용함으로써 피막의 형성이후에도 열산 발생제 또는 열염기 발생제가 피막내에 잔류하지 않아 이로부터 제조된 피막의 물성 저하를 유발하지 않는 장점을 가진다.In addition, since the composition for film formation according to an embodiment of the present invention uses a thermal acid generator or a thermal base generator, the thermal acid generator or thermal base generator does not remain in the film even after the film is formed, and the physical properties of the film produced therefrom are deteriorated. has the advantage of not causing
따라서 본 발명의 일 실시예에 따른 피막형성용 조성물로 형성된 피막은 전자소자의 보호막 또는 절연막으로 극히 우수한 물성을 가진다.Therefore, the film formed from the film-forming composition according to an embodiment of the present invention has excellent physical properties as a protective film or an insulating film for electronic devices.
본 발명은 특정한 구조인 쟌텐 골격 및 실록산 구조를 포함하는 실록산 수지를 포함함으로써 보다 향상된 내열성 및 내구성을 가지는 피막형성용 조성물을 제공하는 것으로, 본 발명의 피막형성용 조성물은,The present invention provides a film-forming composition having improved heat resistance and durability by including a siloxane resin having a specific structure of the janten skeleton and a siloxane structure, the film-forming composition of the present invention,
열산 발생제 또는 열염기 발생제; 및thermal acid generators or thermal base generators; and
하기 화학식 1 및 화학식 2로 표시되는 반복단위를 포함하는 실록산 수지;를 포함한다. A siloxane resin including repeating units represented by Formulas 1 and 2 below.
[화학식 1] [Formula 1]
Figure PCTKR2022013594-appb-img-000003
Figure PCTKR2022013594-appb-img-000003
[화학식 2][Formula 2]
Figure PCTKR2022013594-appb-img-000004
Figure PCTKR2022013594-appb-img-000004
상기 화학식 1 및 화학식 2에서,In Formula 1 and Formula 2,
R1 내지 R4는 서로 독립적으로 수소, (C1-C10)알킬 또는 (C1-C10)알콕시이며;R 1 to R 4 are each independently hydrogen, (C1-C10)alkyl or (C1-C10)alkoxy;
R11 및 R12는 서로 독립적으로 (C1-C10)알킬이며,R 11 and R 12 are each independently (C1-C10)alkyl;
R13 및 R14는 서로 독립적으로 (C6-C12)아릴이며;R 13 and R 14 are each independently (C6-C12)aryl;
p 및 q는 서로 독립적으로 2 내지 10의 정수이며;p and q are independently of each other an integer from 2 to 10;
s 및 t는 몰비로 0.5 ≤ s ≤1.0이며; t는 0 ≤ t ≤ 0.5이다.s and t are 0.5 ≤ s ≤ 1.0 in molar ratio; t is 0 ≤ t ≤ 0.5.
본 발명의 피막형성용 조성물은 종래의 실리콘만을 포함하는 수지와 달리 특정한 구조인 쟌텐 골격을 포함하는 구조단위를 포함하는 실록산 수지를 포함함으로써 투명성이 유지되는 동시에 내열성 및 내구성이 향상된 피막을 형성할 수 있다.Unlike conventional resins containing only silicone, the film-forming composition of the present invention includes a siloxane resin containing a structural unit containing a janten skeleton, which is a specific structure, so that a film with improved heat resistance and durability can be formed while maintaining transparency. there is.
바람직하게 본 발명의 일 실시예에 따른 화학식 1 및 2에서 R1 내지 R4는 수소 또는 (C1-C4)알킬이며; R11 및 R12는 서로 독립적으로 (C1-C4)알킬이며, R13 및 R14는 서로 독립적으로 (C6-C10)아릴이며; p 및 q는 서로 독립적으로 2 내지 5의 정수일 수 있으며, 보다 바람직하게는 R1 내지 R4는 수소 또는 (C1-C3)알킬이며; R11 및 R12는 서로 독립적으로 (C1-C3)알킬일 수 있으며, R13 및 R14는 서로 독립적으로 페닐, 비페닐, 1-나프틸 또는 2-나프틸일 수 있으며, p 및 q는 2 내지 4의 정수일 수 있다.Preferably, R 1 to R 4 in Formulas 1 and 2 according to an embodiment of the present invention are hydrogen or (C1-C4)alkyl; R 11 and R 12 are each independently (C1-C4)alkyl, R 13 and R 14 are independently (C6-C10)aryl; p and q may be each independently an integer of 2 to 5, more preferably R 1 to R 4 are hydrogen or (C1-C3)alkyl; R 11 and R 12 may each independently be (C1-C3)alkyl, R 13 and R 14 may each independently be phenyl, biphenyl, 1-naphthyl or 2-naphthyl, and p and q may be 2 It may be an integer from 4 to 4.
우수한 물성을 가지기위한 측면에서 바람직하게 본 발명의 화학식 1 및 2에서 s 및 t는 0.6≤s≤0.9이며; 0.1≤t≤0.4일 수 있으며, 보다 바람직하게는 0.7≤s≤0.9 이며; 0.1≤t≤0.2일 수 있으며, 보다 좋기로는 0.8≤s≤0.9 이며; 0.1≤t≤0.2일 수 있다. In terms of having excellent physical properties, s and t are preferably 0.6≤s≤0.9 in Formulas 1 and 2 of the present invention; It may be 0.1≤t≤0.4, more preferably 0.7≤s≤0.9; 0.1≤t≤0.2, more preferably 0.8≤s≤0.9; It may be 0.1≤t≤0.2.
바람직하게 본 발명의 화학식 2에서 R11 및 R12는 서로 독립적으로 메틸, 에틸 또는 n-프로필이며, R13 및 R14는 페닐일 수 있다.Preferably, in Formula 2 of the present invention, R 11 and R 12 are each independently methyl, ethyl or n-propyl, and R 13 and R 14 may be phenyl.
본 발명의 일 실시예에 따른 실록산 수지는 중량평균분자량이 5000 내지 200,000g/mol, 바람직하게 10,000 내지 100,000g/mol, 보다 바람직하게는 20,000 내지 100,000g/mol일 수 있다.The siloxane resin according to an embodiment of the present invention may have a weight average molecular weight of 5000 to 200,000 g/mol, preferably 10,000 to 100,000 g/mol, and more preferably 20,000 to 100,000 g/mol.
본 발명의 일 실시예에 따른 실록산 수지는 상기 화학식 1의 반복단위를 가질 수 있는 단량체와 상기 화학식 2의 반복단위를 가질 수 있는 단량체인 하이드로실록산류를 촉매 존재 하에 하이드록시화(hydroxylation)중합 반응으로 제조될 수 있다.The siloxane resin according to an embodiment of the present invention is a hydroxylation polymerization reaction of a monomer that may have a repeating unit of Formula 1 and hydrosiloxanes, which are monomers that may have a repeating unit of Formula 2, in the presence of a catalyst can be manufactured with
구체적으로 본 발명의 일 실시예에 따른 실록산 수지는 상기 화학식 1의 반복단위를 가질 수 있는 단량체와 상기 화학 2의 반복단위를 가질 수 있는 단량체를 중합하여 제조될 수 있다.Specifically, the siloxane resin according to an embodiment of the present invention may be prepared by polymerizing a monomer that may have a repeating unit of Chemical Formula 1 and a monomer that may have a repeating unit of Chemical Formula 2 above.
구체적으로 하기 화학식 1-1의 단위체와 하기 화학식 2-1의 단위체를 중합하여 제조될 수 있다.Specifically, it may be prepared by polymerizing a unit of Formula 1-1 and a unit of Formula 2-1 below.
[화학식 1-1][Formula 1-1]
Figure PCTKR2022013594-appb-img-000005
Figure PCTKR2022013594-appb-img-000005
[화학식 2-1][Formula 2-1]
Figure PCTKR2022013594-appb-img-000006
Figure PCTKR2022013594-appb-img-000006
(상기 화학식 1-1 및 2-1에서,(In Chemical Formulas 1-1 and 2-1,
R1 내지 R4, R11내지 R14, s 및 t는 화학식 1 및 화학식 2에서의 정의와 동일하며, p 및 q는 0 내지 8의 정수이다.)R 1 to R 4 , R 11 to R 14 , s and t are the same as defined in Formulas 1 and 2, and p and q are integers from 0 to 8.)
바람직하게 본 발명의 일 실시예에 따라 제조된 실록산 수지는 하기 화학식 3으로 표시될 수 있다.Preferably, the siloxane resin prepared according to one embodiment of the present invention may be represented by Formula 3 below.
[화학식 3][Formula 3]
Figure PCTKR2022013594-appb-img-000007
Figure PCTKR2022013594-appb-img-000007
(상기 화학식 1-1 및 2-1에서,(In Chemical Formulas 1-1 and 2-1,
R1 내지 R4, R11내지 R14, p, q, s 및 t는 화학식 1 및 화학식 2에서의 정의와 동일하다.)R 1 to R 4 , R 11 to R 14 , p, q, s and t are the same as defined in Formulas 1 and 2.)
본 발명의 일 실시예에 따른 실록산 수지는 교대공중합체, 랜덤공중합체 등을 모두 포함한다.The siloxane resin according to an embodiment of the present invention includes both alternating copolymers and random copolymers.
본 발명의 실록산 수지는 촉매 존재 하에 제조될 수 있으며, 이때 사용되는 촉매는 한정이 있는 것은 아니나, 일례로 백금(백금흑을 포함), 로듐, 팔라듐 등의 백금족 금속 단체; H2PtCl4·nH2O, H2PtCl6·nH2O, NaHPtCl6·nH2O, KHPtCl6·nH2O, Na2PtCl6·nH2O, K2PtCl4·nH2O, PtCl4·nH2O, PtCl2, Na2HPtCl4·nH2O(식 중, n은 0∼6인 정수가 바람직하며, 특히 0 이나 6이 바람직함) 등의 염화백금, 염화백금산 및 염화백금산염; 로듐-올레핀 복합체; 클로로트리스(트리페닐포스핀)로듐(이른바 윌킨슨 촉매);염화백금, 염화백금산이나 염화백금산염과 비닐기 함유 실록산(특히 비닐기 함유 환형 실록산)의 복합체 등을 들 수 있다.The siloxane resin of the present invention can be prepared in the presence of a catalyst, and the catalyst used in this case is not limited, but examples thereof include platinum group metals such as platinum (including platinum black), rhodium, and palladium; H 2 PtCl 4 nH 2 O, H 2 PtCl 6 nH 2 O, NaHPtCl 6 nH 2 O, KHPtCl 6 nH 2 O, Na 2 PtCl 6 nH 2 O, K 2 PtCl 4 nH 2 O, PtCl 4 nH 2 O, PtCl 2 , Na 2 HPtCl 4 nH 2 O (in the formula, n is preferably an integer of 0 to 6, particularly preferably 0 or 6) Platinum chloride, chloroplatinic acid and chloride platinate; rhodium-olefin complex; Chlorotris(triphenylphosphine)rhodium (so-called Wilkinson's catalyst); Platinum chloride, chloroplatinic acid or chloroplatinic acid, and a composite of vinyl group-containing siloxane (especially vinyl group-containing cyclic siloxane); and the like.
본 발명의 실록산 수지의 중합 반응에 있어서 필요에 따라 유기 용제가 사용될 수 있다. 유기 용제로서는 일례로 톨루엔, 크실렌 등의 탄화수소계 유기 용제가 바람직하다.In the polymerization reaction of the siloxane resin of the present invention, an organic solvent may be used if necessary. As the organic solvent, for example, hydrocarbon-based organic solvents such as toluene and xylene are preferable.
중합 조건으로서, 중합 온도는 예를 들면 40∼150℃, 특히 80∼120℃가 바람직하다. 중합 온도가 지나치게 낮으면 중합 완결까지 장시간을 요하는 경우가 있고, 반대로 중합 온도가 지나치게 높으면 촉매가 활성화되지 않을 우려가 있다. 또, 중합 시간은 중합물의 종류 및 양에도 의존하지만, 중합계 내에 습기의 개입을 방지하기 위해, 약 0.5∼10시간, 특히 0.5∼5시간 이내로 종료하는 것이 바람직하다. 또, 유기 하이드로실록산류는 부반응인 불균화 반응을 일으키기 쉽고, 또한 하이드록시화 중합 반응은 일반적으로 발열 반응이기 때문에, 상기 유기 하이드로실록산류를 적하에 의해 첨가하는 것이 바람직하다.As polymerization conditions, the polymerization temperature is, for example, 40 to 150°C, particularly preferably 80 to 120°C. If the polymerization temperature is too low, it may take a long time to complete polymerization, and if the polymerization temperature is too high, the catalyst may not be activated. The polymerization time depends on the type and amount of the polymer, but is preferably completed within about 0.5 to 10 hours, particularly within 0.5 to 5 hours, in order to prevent moisture from entering the polymerization system. In addition, organic hydrosiloxanes tend to cause disproportionation reactions as side reactions, and since hydroxylation polymerization reactions are generally exothermic reactions, it is preferable to add the organic hydrosiloxanes dropwise.
본 발명의 실록산 수지는 특정한 구조인 쟌텐을 가지는 동시에 하이드록실록산류의 치환기의 함량을 조절함으로써 보다 내성이 우수하며, 내수성, 내산성 및 내알칼리성을 가진다.The siloxane resin of the present invention has a specific structure of janten, and at the same time, by adjusting the content of substituents of hydroxyloxanes, it has more excellent resistance, water resistance, acid resistance and alkali resistance.
따라서 본 발명의 실록산 수지는 보호막 또는 절연막 형성에 매우 유용하다.Therefore, the siloxane resin of the present invention is very useful for forming a protective film or an insulating film.
본 발명의 실록산 수지는 실록산 수지 조성물 총중량에 대해 30 내지 70중량%, 바람직하게 35 내지 65중량%, 보다 바람직하게는 40 내지 60중량%일 수 있다.The siloxane resin of the present invention may be 30 to 70% by weight, preferably 35 to 65% by weight, more preferably 40 to 60% by weight based on the total weight of the siloxane resin composition.
이하에서는 본 발명의 일 실시예에 따른 열산 발생제 및 열염기 발생제에 대해 상세하게 설명한다.Hereinafter, a thermal acid generator and a thermal base generator according to an embodiment of the present invention will be described in detail.
본 발명의 일 실시예에 따른 열산 발생제 및 열염기 발생제는 본 발명의 기술분야에서 사용되는 것이라면 모두 가능하나, 본 발명의 실록산 수지와의 바람직한 조합의 측면에서 있어서 열산 발생제는 Bis(4-t-부틸페닐이오도니움)트리플루오로메타네술포네이트(Bis (4-tbutylphenyl iodonium) trifluoromethanesulfonate)), 트리아릴술포니움헥사플루오로안디모네이트 (Triarylsulfoniumhexafluoroantimonate), 트리아릴술포니움헥사플로오로포스페이트 (Triarylsulfoniumhexafluorophosphate), 테트라메틸암모늄트리플루오로메타네술포네이트(Tetramethylammoniumtrifluoromethanesulfonate) 및 트리에틸암네플루오로설페이트 (Triethylamnefluorosulfate)중에서 선택되는 하나 또는 둘 이상이며;The thermal acid generator and the thermal base generator according to an embodiment of the present invention can be used as long as they are used in the technical field of the present invention, but in terms of a preferred combination with the siloxane resin of the present invention, the thermal acid generator is Bis (4 -t-butylphenyliodonium)trifluoromethanesulfonate (Bis (4-tbutylphenyl iodonium) trifluoromethanesulfonate), triarylsulfoniumhexafluoroantimonate, triarylsulfonium hexafluoro one or two or more selected from triarylsulfoniumhexafluorophosphate, tetramethylammoniumtrifluoromethanesulfonate, and triethylamnefluorosulfate;
상기 열염기 발생제는 테트라메틸암모늄아세테이트(Tetramethylammoniumacetate), 테트라메틸암모늄옥틸레이트(Tetramethylammoniuoctylate), 테트라부틸암모늄아세테이트(Tetrabutylammoniumacetate), 테트라부틸암모늄옥틸레이트(Tetrabutylammoniumoctylate), 트리메틸벤질암모늄아세테이트(Trimethylbenzylammoniumacetate), 아자비시클로운데센포르메이트(Azabicycloundeceneformate) 및 트리에틸아민p-톨루엔술포네이트(Triethylamine p-toluenesulfonate) 중에서 선택되는 하나 또는 둘 이상일 수 있다.The thermal base generator is tetramethylammoniumacetate, tetramethylammoniumoctylate, tetrabutylammoniumacetate, tetrabutylammoniumoctylate, trimethylbenzylammoniumacetate, azabicyclo It may be one or two or more selected from undeceneformate (Azabicycloundeceneformate) and triethylamine p-toluenesulfonate.
본 발명의 일 실시예에 따른 열산 발생제 또는 열염기 발생제는 실록산 수지 100중량부에 대하여 0.01 ~ 10중량부, 구체적으로 0.05 내지 10중량부, 보다 구체적으로 0.1 내지 8중량부로 사용될 수 있다.The thermal acid generator or thermal base generator according to an embodiment of the present invention may be used in an amount of 0.01 to 10 parts by weight, specifically 0.05 to 10 parts by weight, and more specifically 0.1 to 8 parts by weight, based on 100 parts by weight of the siloxane resin.
바람직하게 본 발명의 일 실시예에 따른 열산 발생제는 50 내지 250℃의 온도범위에서 강산 및 강염기를 발생한다. 따라서 본 발명의 일 실시예에 따른 열산 발생제 또는 열염기 발생제는 본 발명의 일 실시예에 따른 실록산 수지를 50℃이상의 온도에서 가열함에 따라, 20 ~ 250℃의 범위에서 휘발되는 강산을 발생하는 열산 발생제, 또는 20 ~ 250℃의 범위에서 휘발되는 강염기를 발생하는 열염기 발생제일 수 있다.Preferably, the thermal acid generator according to an embodiment of the present invention generates a strong acid and a strong base in a temperature range of 50 to 250 °C. Therefore, the thermal acid generator or thermal base generator according to an embodiment of the present invention generates a strong acid volatilized in the range of 20 to 250 ° C as the siloxane resin according to an embodiment of the present invention is heated at a temperature of 50 ° C or higher. It may be a thermal acid generator to generate a strong base volatilized in the range of 20 ~ 250 ℃, or a thermal base generator.
본 발명의 일 실시예에 따른 피막형성용 조성물에는 (메타)아크릴산에스테르를 더 포함할 수 있다. 본 발명의 일 실시예에 따른 피막형성용 조성물에 (메타)아크릴산에스테르를 첨가함으로써 형성된 피막의 투명성을 최대한 유지시키고, 피막형성용 조성물의 열경화성을 부여할 수 있다. 나아가 첨가되는 (메타)아크릴산에스테르의 종류에 따라 형성되는 피막의 유연성, 경도 및 인성을 제어할 수 있으며, 피막의 굴절율이나 내연성의 제어가 가능한 장점을 가진다.The film-forming composition according to an embodiment of the present invention may further include (meth)acrylic acid ester. By adding (meth)acrylic acid ester to the composition for forming a film according to an embodiment of the present invention, transparency of the formed film can be maintained to the maximum and thermosetting properties of the composition for film formation can be imparted. Furthermore, flexibility, hardness and toughness of the formed film can be controlled according to the type of (meth)acrylic acid ester added, and the refractive index or flame resistance of the film can be controlled.
본 발명의 일 실시예에 따른 (메타)아크릴산에스테르의 구체적인 일례는, 메틸메타크릴레이트(Methyl methacrylate), 메틸아크릴레이트(Methyl acrylate), 에틸아크릴레이트(Ethyl acrylate), 에틸메타크릴레이트(Ethyl methacrylate), 부틸메타크릴레이트(Butyl methacrylate), 부틸아크릴레이트(Butyl acrylate), 2-에틸헥실아크릴레이트(2-ethylhexyl acrylate), 하이드록시에틸아크릴레이트 (Hydroxyethyl acrylate), 벤질아크릴레이트(Benzyl acrylate), 페녹시에틸아크릴레이트(Phenoxyethyl acrylate), 테트라하이드로펄퍼릴아크릴레이트(Tetrahydrofurfulyl acrylate), 페닐아크릴레이트(phenyl acrylate), 나프틸아크릴레이트(naphtyl acrylate), 페난티릴아크릴레이트(Phenanthlyl acrylate) 등의 단관능 (메타)아크릴산에스테르, 에틸렌글리콜디아크릴레이트(Ethylene glycol diacrylate), 프로필렌글리콜디아크릴레이트(Propylene glycol diacrylate), 디에틸렌글리콜디아크릴레이트(Diethyleneglycoldiacrylate), 디프로필렌글리콜디아크릴레이트(Dipropylene glycol diacrylate), 헥산디올디아크릴레이트(Hexane dioldiacrylate, HDDA), 폴리에틸렌글리콜 디아크릴레이트(Polyethylene glycol diacrylate), 폴리프로필렌글리콜디아크릴레이트(Polypropylene glycol diacrylate), 비스페놀-A디아크릴레이트(Bisphenol-A diacrylate), 비스페놀-A에톡실레이티드디아크릴레이트(Bisphenol-A ethoxylated diacrylate), 플루오렌비스페놀디아크릴레이트(Fluorene bisphenol diacrylate), 아 다만틸비스페놀디아크릴레이트(Adamantyl bisphenol diacrylate) 등의 ２관능(메타)아크릴산에스테르, 글리세린트리아크릴레이트(Glycerin triacrylate), 트리메티롤프로판트리아크릴레이트(Trimethylolpropane triacrylate, TMPTA), 트리메티롤프로판에톡실레이티드트리아크릴레이트(Trimethylol propane ethoxylated triacrylate), 펜타에리트리톨트리아크릴레이트(Pentaerythritol triacrylate), 디트리메티롤프로판트리아크릴레이트(Ditrimethylolpropane triacrylate)등의 ３관능(메타)아크릴산에스테르, 디트리메티롤프로판테트라아크릴레이트(Di trimethylolpropane tetraacrylate), 디펜타에리트리톨헥사아크릴레 이트펜타아크릴레이트(Dipentaerythritol hexaacrylate pentaacrylate,DTPA), 디펜타에리트리톨헥사아크릴 레이트(Dipentaerythritolhexaacrylate, DPHA)등의 4관능 이상의 (메타)아크릴산에스테르를 들 수 있다. 바람직하게 단관능성 (메타)아크릴산에스테르를 사용하는 것 보다는 2관능성 이상의 다가 알코올 (메타)아크릴산에스테르를 사용함이 보다 바람직하다. A specific example of the (meth)acrylic acid ester according to an embodiment of the present invention is methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate ), Butyl methacrylate, Butyl acrylate, 2-ethylhexyl acrylate, Hydroxyethyl acrylate, Benzyl acrylate, Phenoxyethyl acrylate, tetrahydrofurfulyl acrylate, phenyl acrylate, naphthyl acrylate, phenanthryl acrylate, etc. Functional (meth)acrylic acid ester, ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate , Hexane dioldiacrylate (HDDA), Polyethylene glycol diacrylate, Polypropylene glycol diacrylate, Bisphenol-A diacrylate, Bisphenol -A ethoxylated diacrylate (Bisphenol-A ethoxylated diacrylate), fluorene bisphenol diacrylate (Fluorene bisphenol diacrylate), adamantyl bisphenol diacrylate (Adama Bifunctional (meth)acrylic acid esters such as ntyl bisphenol diacrylate), glycerin triacrylate, trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxylated triacrylate (Trimethylol trifunctional (meth)acrylic acid esters such as propane ethoxylated triacrylate, pentaerythritol triacrylate, ditrimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate ), tetrafunctional or higher functional (meth)acrylic acid esters such as dipentaerythritol hexaacrylate pentaacrylate (DTPA) and dipentaerythritolhexaacrylate (DPHA). Preferably, it is more preferable to use a polyhydric alcohol (meth)acrylic acid ester having more than two functional properties rather than using a monofunctional (meth)acrylic acid ester.
본 발명의 일 실시예에 따른 피막형성용 조성물은 광라디칼발생제 또는 열라디칼발생제를 더 포함할 수 있다. 광라디칼발생제 또는 열라디칼발생제를 포함함으로써 라디칼에 의해 경화를 촉진시킬 수 있다.The film-forming composition according to an embodiment of the present invention may further include an optical radical generator or a thermal radical generator. By including an optical radical generator or a thermal radical generator, curing can be accelerated by radicals.
본 발명의 일 실시예에 따른 광라디칼발생제의 일례로는 tert-부틸퍼옥시-iso-부틸레이트, 2,5-디메틸-2,5-비스(벤조일디옥시)헥산, 1,4-비스[α-(tert-부틸디옥시)-iso-프로폭시]벤젠, 디-tert-부틸퍼옥시드, 2,5-디메틸-2,5-비스(tert-부틸디옥시)헥센하이드로퍼옥사이드, α-(iso-프로필페닐)-iso-프로필하이드로퍼옥사이드, tert-부틸하이드로퍼옥사이드, 1,1-비스(tert-부틸디옥시)-3,3,5-트리메틸시클로헥산, 부틸-4,4-비스(tert-부틸디옥시)발레레이트, 시클로헥사논퍼옥사이드, 2,2',5,5'-테트라(tert-부틸퍼옥시카르보닐)벤조페논, 3,3',4,4'-테트라(tert-부틸퍼옥시카르보닐)벤조페논, 3,3',4,4'-테트라(tert-아밀퍼옥시카르보닐)벤조페논, 3,3',4,4'-테트라(tert-헥실퍼옥시카르보닐)벤조페논, 3,3'-비스(tert-부틸퍼옥시카르보닐)-4,4'-디카르복시벤조페논, tert-부틸퍼옥시벤조에이트, 디-tert-부틸디퍼옥시이소프탈레이트 등의 유기과산화물; 9,10-안트라퀴논, 1-클로로안트라퀴논, 2-클로로안트라퀴논, 옥타메틸안트라퀴논, 1,2-벤즈안트라퀴논 등의 퀴논류; 벤조인메틸, 벤조인에틸에테르, α-메틸벤조인, α-페닐벤조인 등의 벤조인유도체; 2,2-디메톡시-1,2-디페닐에탄-1-온, 1-하이드록시-시클로헥실-페닐-케톤, 2-하이드록시-2-메틸-1-페닐-프로판-1-온, 1-[4-(2-하이드록시에톡시)-페닐]-2-하이드록시-2-메틸-1-프로판-1-온, 2-하이드록시-1-[4-{4-(2-하이드록시-2-메틸-프로피오닐)벤질}-페닐]-2-메틸-프로판-1-온, 페닐글리옥실릭애씨드메틸에스테르, 2-메틸-1-[4-(메틸티오)페닐]-2-모르폴리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-모르폴리노페닐)-1-부탄온, 2-디메틸아미노-2-(4-메틸-벤질)-1-(4-모르폴린-4-일-페닐)-부탄-1-온 등의 알킬페논계 화합물; 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드, 2,4,6-트리메틸벤조일-디페닐-포스핀옥사이드 등의 아실포스핀옥사이드계 화합물; 1-[4-(페닐티오)페닐]-1,2-옥탄디온2-(O-벤조일옥심), 1-[9-에틸-6-(2-메틸벤조일)-9H-카바졸-3-일]에탄온O-아세틸옥심 등의 옥심에스테르계 화합물을 들 수 있다.Examples of the photoradical generator according to an embodiment of the present invention include tert-butylperoxy-iso-butylate, 2,5-dimethyl-2,5-bis (benzoyldioxy) hexane, 1,4-bis [α-(tert-butyldioxy)-iso-propoxy]benzene, di-tert-butylperoxide, 2,5-dimethyl-2,5-bis(tert-butyldioxy)hexenehydroperoxide, α -(iso-propylphenyl)-iso-propylhydroperoxide, tert-butylhydroperoxide, 1,1-bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, butyl-4,4 -bis(tert-butyldioxy)valerate, cyclohexanone peroxide, 2,2',5,5'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'- Tetra (tert-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert-amylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (tert- Hexylperoxycarbonyl)benzophenone, 3,3'-bis(tert-butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tert-butylperoxybenzoate, di-tert-butyldiperoxy organic peroxides such as isophthalate; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, and 1,2-benzanthraquinone; benzoin derivatives such as benzoin methyl, benzoin ethyl ether, α-methylbenzoin, and α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2- Hydroxy-2-methyl-propionyl)benzyl}-phenyl]-2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-dimethylamino-2-(4-methyl-benzyl) Alkylphenone compounds, such as -1-(4-morpholin-4-yl-phenyl)-butan-1-one; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- oxime ester compounds such as yl]ethanone O-acetyl oxime.
광라디칼 발생제는, 시판품으로서 입수가 가능하며, 예를 들어, IRGACURE(등록상표) 651, IRGACURE 184, IRGACURE 500, IRGACURE 2959, IRGACURE 127, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE 379EG, IRGACURE 819, IRGACURE 819DW, IRGACURE 1800, IRGACURE 1870, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250, IRGACURE 1173, IRGACURE MBF, IRGACURE TPO, VICURE-10, VICURE-55(이상, STAUFFER Co.LTD제), ESACURE KIP150, ESACURE TZT, ESACURE 1001, ESACURE KTO46, ESACURE KB1, ESACURE KL200, ESACURE KS300, ESACURE EB3, 트리아진-PMS, 트리아진A, 트리아진B(이상, 일본사이버헤그너(주)제), 아데카옵토머 N-1717, 아데카옵토머 N-1414, 아데카옵토머 N-1606(이상, (주)ADEKA제)을 들 수 있다.Photoradical generators can be obtained as commercial products, for example, IRGACURE (registered trademark) 651, IRGACURE 184, IRGACURE 500, IRGACURE 2959, IRGACURE 127, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE 379EG , IRGACURE 819, IRGACURE 819DW, IRGACURE 1800, IRGACURE 1870, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250, IRGACURE 1173, IRGACURE MBF, IRGACURE TPO, VICURE-10, VICURE-55 (above, manufactured by STDAUFFER Co.) , ESACURE KIP150, ESACURE TZT, ESACURE 1001, ESACURE KTO46, ESACURE KB1, ESACURE KL200, ESACURE KS300, ESACURE EB3, Triazine-PMS, Triazine A, Triazine B (above, manufactured by Cyber Hegner Co., Ltd., Japan), Adeka optomer N-1717, Adeka optomer N-1414, and Adeka optomer N-1606 (above, made by ADEKA Corporation) are mentioned.
열라디칼발생제의 일례는, 에폭시아크릴레이트올리고머, 우레탄아크릴레이트올리고머, 폴리에스테르아크릴레이트올리고머, 실리콘아크릴레이트올리고머, 노보락수지아크릴레이트 등 분자량 3,000 ~ 100,000의 올리고머를 들 수 있다. Examples of the thermal radical generating agent include oligomers having a molecular weight of 3,000 to 100,000, such as epoxy acrylate oligomer, urethane acrylate oligomer, polyester acrylate oligomer, silicone acrylate oligomer, and novolak resin acrylate.
본 발명의 일 실시예에 따른 피막형성 조성물은 추가 첨가제를 더 포함할 수 있으며, 추가 첨가제는 용제, 다른 유기수지, 가교제, 용매, 실리카, 계면활성제, 염료, 점도조절제, 소포제 등일 수 있다. 구체적으로 용제는 에탄올이나 2프로판올처럼 알코올계, 메틸에틸케톤이나 아세톤과 같은 케톤류일 수 있다. 유기수지로는 용매가용성의 알키드 수지, 아크릴 수지, 에폭시 수지, 우레탄 수지 등일 수 있다. 가교제로는 폴리아크릴레이트모노머나 아크릴이 가교된 이소시아누릭산 등을 사용될 수 있다. The film-forming composition according to an embodiment of the present invention may further include additional additives, and the additional additives may include solvents, other organic resins, crosslinking agents, solvents, silica, surfactants, dyes, viscosity modifiers, and antifoaming agents. Specifically, the solvent may be alcohols such as ethanol or 2-propanol, or ketones such as methyl ethyl ketone or acetone. The organic resin may be a solvent-soluble alkyd resin, an acrylic resin, an epoxy resin, or a urethane resin. As the crosslinking agent, a polyacrylate monomer or isocyanuric acid crosslinked with acrylic may be used.
본 발명의 피막형성용 조성물은 유기용매를 더 포함할 수 있으며, 본 기술분야에서 당업자가 인식할 수 있는 범위에서 사용가능한 유기용매라면 모두 가능하나, 일례로 메탄올, 에탄올, 1-프로판올, 2-프로판올, 1-부탄올, 2-부탄올, sec-부탄, 1-펜타놀, 2-메틸부탄올, 3-메틸부탄올, 2-펜타놀, 4-메틸-2-펜타놀, 사이클로헥사놀, 메틸사이클로헥사놀, n-헥사놀, 퍼퓨릴알코올, 퍼퓨릴메탄올, 테트라하이드로퍼퓨릴알콜, 벤질알콜 등 알코올류; 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 메틸n-부틸케톤, 메틸t-부틸케톤, 메틸n-펜틸케톤, 메틸n-헥실케톤, 디에틸케톤, 디이소프로필케톤, 디이소부틸케톤, 시클로펜타논, 시클로헥사논, 메틸시클로헥사논, 시클로헵타논, 시클로옥타논, 2,4-펜타네디온, 2,5-헥사디온, 아세토 페논 등 케톤류; n-펜탄, 이소펜탄, n-헥산, 이소헥산, n-헵탄, 이소헵탄, 옥탄, 이소옥탄, 2,2,4-트리에틸펜탄, 시클로헥산, 메틸시클로헥산, 벤젠, 톨루엔, 자일렌, 트리에틸벤젠, 에틸벤젠, 메틸에틸벤젠, n-프로필벤젠, 이소프로필벤젠, 펜틸벤젠, 디에틸벤젠, 이소부틸벤젠, 트리에틸벤젠, 디이소프로필벤젠 등 하이드로카본류; 테트라하이드로퓨란, 2-메틸테트라하이드로퓨란, 디에틸에테르, 디-n-프로필에테르, 디-이소프로필에테르, 디-n-부틸에테르, 디이소부틸에테르, 디-n-헥실에테르, 아니솔, 페네톨, 디페닐에테르, 에틸벤질에테르, bis(2-에틸헥실)에테르, 에필렌옥사이드, 1,2-프로필렌옥사이드, 1,4-디옥산, 4-메틸디옥솔레인, 디메틸디옥솔레인, 그레실메틸에테르, 디벤질에테르, 부틱페닐에테르 등 에테르류; 메틸아세테이트, 에틸아세테이트, n-프로필아세테이트, 이소프로필아세테이트, n-부틸아세테이트, 이소부틸아세테이트, sec-부틸아세테이트, n-펜 틸아세테이트, sec-펜틸아세테이트, 메틸펜틸아세테이트, 2-에틸부틸아세테이트, 2-에틸헥실아세테이트, 벤질아세테이트, 시클로헥실아세테이트, 메틸시클로헥실아세테이트, n-노닐아세테이트, 메틸아세토아세테이트, 에틸아세토아세테이트, 에틸프로피오네이트, n-부틸프로피오네이트, 이소아밀프로피오네이트, 메틸피루베이트, 에틸피루베이트, 디에틸옥살레이트, 디-n-부틸옥살레이트, 메틸락테이트, 에틸락테이트, 부틸락테이트, n-펜틸락테이트, 메틸메톡시프로피오네이트, 에틸에톡시프로피오네이트, 디에틸말로네이트, 디메틸프탈레이트, 디에틸프탈레이트, 디에틸카보네이트, 프로필렌카보네이트 등 에스테르류; 감마-부티롤락톤, 감마-발레롤락톤, 델타-발레롤 락톤 등 락톤류; 아세토니트릴, 프로피오노니트릴, 아크릴로니트릴 등 니트릴류, 에틸렌글리콜, 프로필렌글리콜, 1,2-부타네디올, 1,3-부타네디올, 1,2-펜탄세디올, 2,4-펜탄디올, 2-메틸펜탄-2,4-디올, 2,5- 헥사네디올, 2,4-헵타네디올, 2-에틸헥산-1,3-디올, 디에틸렌글리콜, 디프로필렌글리콜, 트리에틸렌글리콜, 트 리프로필렌글리콜 등 글리콜류; 하이드록시아세톤(아세톨), 3-하이드록시-3-메틸-2-부타논, 4-하이드록시-3-메 틸-2-부타논, 5-하이드록시-2-펜타논, 4-하이드록시-4-메틸-2-펜타논 등 하이드록시케톤류; 글리콜에테르류로서, 에틸렌글로콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜모노프로필에테르, 에틸렌글리콜모노n-부틱에테르, 에틸렌글리콜모노n-펜틸에테르, 에틸렌글리콜모노n-헥실에테르, 에틸렌글리콜모노2-에틸부틸에테르, 에틸렌글리콜모노2-에틸헥실에테르, 에틸렌글리콜모노페닐에테르 등 에틸렌글리콜모노에테르류; 에틸렌글리콜디메틸에테르, 에틸렌글리콜디에틸에테르, 에틸렌글리콜메틸에틸에테르, 에틸렌글리콜디부틸에테르 등 에틸렌글리콜디에테르류; 에틸렌글리콜모노메틸에테르아세테이트, 에틸렌글리콜모노에틸에테르아세테이트, 에틸렌글리콜모노프로필에테르아세테이트, 에틸렌글리콜모토n-부틸에테르아세테이트, 에틸렌글리콜디아세테이트 등 에틸렌글리콜아세테이트류; 프로필렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르, 프로필렌 글리콜모노n-프로필에테르, 프로필렌글리콜모노n-부틸에테르, 프로필렌글리콜모노t-부틸에테르 등 프로필렌글리콜모노에테르류, 프로필렌글리콜디메틸에테르, 프로필렌글리콜디에틸에테르, 프로필렌글리콜메틸에틸에테르 등 프로필렌글리콜디에테르류; 프로필렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노에틸에테르아세테이트, 프로필렌글리콜모노n-프로필에테르아세테이트, 프로필렌글리콜모노n-부틸에테르아세테이트, 프로필렌글리콜디아세테이트 등 프로필렌글리콜아세테이트류; 3-메톡시-1-부탄올, 3-메톡시부틸아세테이트, 3-메틸-3-메톡시-1-부탄올, 3-메톡시-1-부틸아세테이트, 3-메틸-3-메톡시-1-부틸아세테이트 등 부틸렌글리콜유도체, 디에틸글리콜모 노메틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노프로필에테르, 디에틸렌글리콜모노n-부틸에테르, 디에틸렌글리콜모노n-헥실에테르 등 디에틸글리콜모노에테르류; 디에틸렌글리콜디메틸에테르, 디에틸렌글리 콜메틸에틸에테르류, 디에틸렌글리콜디에틸에테르 등 디에틸렌글리콜디에테르류; 디에틸렌글리콜모노메틸에테르아세테이트, 디에틸렌글리콜모노에틸에테르아세테이트, 디에틸렌글리콜모노프로필에테르아세테이트, 디에틸렌글리콜모노n-부틸에테르아세테이트 등 디에틸렌글리콜아세테이트류; 디프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노에틸에테르, 디프로필렌글리콜모노프로필에테르 등 디프로필렌글리콜모노에테르류; 디프로필렌글리콜디메틸에테르 등 디프로필렌글리콜디에테르류; 디프로필렌글리콜모노메틸에테르, 트리에틸렌글리콜모노에틸에테르, 트리실렌글리콜모노메틸에테르아세테이트, 트리프로필렌글리콜모노메틸에테르, 트리프로필렌글리콜모노메틸에테르아세테이트, 테트라에틸렌글리콜디-n-부틸에테르 등 디프로필렌글리콜아세테이트류; 불균질화합물로서, N-메틸피롤리디논, N,N-디메틸이마이드아졸리디논, 포름이마이드, N-메틸포름아미드, N-에틸포름아미드, N,N-디메틸포름아미드, N,N-디에틸포름아미드, N-메틸아세타마이드, N,N-디메틸아세트아미드, N,N-디에틸아세트아미드, N-메틸프로피온아미드, N,N-디메틸술프옥사이드, 술포레인, 1,3-프로페인술톤 등이 있다. 바람직하게는 에탄올, 2-프로판올 및 세크부틸알콜에서 선택되는 어느 하나 또는 둘이상과 프로필렌 글리콜 모노메틸에테르, 프로필렌 글리콜 모노메틸에테르 아세테이트 및 메틸이소부틸케톤, n-프로필 아세테이트로에서 선택되는 어느 하나 또는 둘이상의 혼합물일 수 있다. The film-forming composition of the present invention may further include an organic solvent, and any organic solvent that can be used within the range recognized by those skilled in the art is possible, but for example, methanol, ethanol, 1-propanol, 2- Propanol, 1-butanol, 2-butanol, sec-butane, 1-pentanol, 2-methylbutanol, 3-methylbutanol, 2-pentanol, 4-methyl-2-pentanol, cyclohexanol, methylcyclohexa alcohols such as nol, n-hexanol, furfuryl alcohol, furfuryl methanol, tetrahydrofurfuryl alcohol, and benzyl alcohol; Acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, methyl t-butyl ketone, methyl n-pentyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclo ketones such as pentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2,4-pentanedione, 2,5-hexadione, and acetophenone; n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, octane, isooctane, 2,2,4-triethylpentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, tri hydrocarbons such as ethylbenzene, ethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, pentylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene and diisopropylbenzene; Tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, di-n-propyl ether, di-isopropyl ether, di-n-butyl ether, diisobutyl ether, di-n-hexyl ether, anisole, phenetol, diphenyl ether, ethylbenzyl ether, bis(2-ethylhexyl) ether, epylene oxide, 1,2-propylene oxide, 1,4-dioxane, 4-methyldioxolane, dimethyldioxolane, ethers such as greymethyl ether, dibenzyl ether, and butic phenyl ether; Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethyl propionate, n-butyl propionate, isoamylpropionate, methyl Pyruvate, ethylpyruvate, diethyloxalate, di-n-butyloxalate, methyl lactate, ethyl lactate, butyl lactate, n-pentyl lactate, methylmethoxypropionate, ethylethoxypropio esters such as nate, diethyl malonate, dimethyl phthalate, diethyl phthalate, diethyl carbonate, and propylene carbonate; lactones such as gamma-butyrolactone, gamma-valerollactone, and delta-valerollactone; Nitriles such as acetonitrile, propiononitrile, and acrylonitrile, ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 2,4-pentanediol , 2-methylpentane-2,4-diol, 2,5-hexanediol, 2,4-heptanediol, 2-ethylhexane-1,3-diol, diethylene glycol, dipropylene glycol, triethylene glycol , glycols such as tripropylene glycol; Hydroxyacetone (acetol), 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy hydroxy ketones such as oxy-4-methyl-2-pentanone; As glycol ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monon-butic ether, ethylene glycol monon-pentyl ether, ethylene glycol monon-hexyl ether, ethylene ethylene glycol monoethers such as glycol mono2-ethylbutyl ether, ethylene glycol mono2-ethylhexyl ether, and ethylene glycol monophenyl ether; ethylene glycol diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol dibutyl ether; ethylene glycol acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol mono-butyl ether acetate, and ethylene glycol diacetate; Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, propylene glycol monoethers, propylene glycol dimethyl ether, propylene glycol di propylene glycol diethers such as ethyl ether and propylene glycol methyl ethyl ether; propylene glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monon-propyl ether acetate, propylene glycol monon-butyl ether acetate, and propylene glycol diacetate; 3-methoxy-1-butanol, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butanol, 3-methoxy-1-butylacetate, 3-methyl-3-methoxy-1- Butylene glycol derivatives such as butyl acetate, diethyl glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, etc. glycol monoethers; diethylene glycol diethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether; diethylene glycol acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, and diethylene glycol monon-butyl ether acetate; dipropylene glycol monoethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether; dipropylene glycol diethers such as dipropylene glycol dimethyl ether; Dipropylene glycol, such as dipropylene glycol monomethyl ether, triethylene glycol monoethyl ether, trisilene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether acetate, tetraethylene glycol di-n-butyl ether, etc. acetates; As heterogeneous compounds, N-methylpyrrolidinone, N,N-dimethylimideazolidinone, formimide, N-methylformamide, N-ethylformamide, N,N-dimethylformamide, N,N -Diethylformamide, N-methylacetamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylpropionamide, N,N-dimethylsulfoxide, sulfolane, 1, and 3-propane sultone. Preferably, any one or two or more selected from ethanol, 2-propanol and secbutyl alcohol, and any one or more selected from propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, and n-propyl acetate It may be a mixture of two or more.
이하 본 발명의 일 실시예에 따른 피막형성용 조성물을 제조하기 위한 실시예는 다음과 같다. 그러나, 이는 단지 본 발명의 일 실시예일 뿐이므로, 본 발명이 이에 한정되는 것은 아니다. Hereinafter, an example for preparing a composition for forming a film according to an embodiment of the present invention is as follows. However, since this is only one embodiment of the present invention, the present invention is not limited thereto.
[제조예 1] 디하이드로실록산 화합물의 합성 [Preparation Example 1] Synthesis of dihydrosiloxane compound
3000ml 삼구 라운드 플라스크에 1,3-디하이드로-1,1,3,3-테트라메틸디실록산과 1,3-디하이드로-1,1,3,3-테트라페놀디실록산을 4:1의 몰비로 첨가하여 하기 화학식 2-2로 표시되며 n이 15인 디하이드로실록산 화합물 1을 제조하였다.In a 3000ml three-necked round flask, 1,3-dihydro-1,1,3,3-tetramethyldisiloxane and 1,3-dihydro-1,1,3,3-tetraphenoldisiloxane were mixed at a molar ratio of 4:1. was added to prepare a dihydrosiloxane compound 1 represented by the following Chemical Formula 2-2 and having n=15.
[화학식 2-2][Formula 2-2]
Figure PCTKR2022013594-appb-img-000008
Figure PCTKR2022013594-appb-img-000008
[실시예 1] 실록산 수지의 제조[Example 1] Preparation of siloxane resin
3000ml 삼구 라운드 플라스크에 스피로[플루오렌-9,9’-잔텐]-3’,6’-비스(1-프로펜)(spiro[fluorine-9,9'-xanthene]-3',6'-bis(1-propen)) 44.0g, 톨루엔 60g 및 염화백금산 0.1g을 첨가하여 80℃로 온도를 높였다.Spiro[fluorine-9,9'-xanthene]-3',6'-bis(1-propene) (spiro[fluorine-9,9'-xanthene]-3',6'- 44.0 g of bis(1-propen)), 60 g of toluene and 0.1 g of chloroplatinic acid were added to raise the temperature to 80°C.
그 후, 상기 플라스크 내에 제조예 1에서 제조된 디하이드로실록산 화합물 12.8g을 적하하였다. 적하 후, 100℃에서 1시간 교반시킨 후, 톨루엔을 제거하여 49g의 고체 생성물을 얻었다.Thereafter, 12.8 g of the dihydrosiloxane compound prepared in Preparation Example 1 was added dropwise into the flask. After dripping, after stirring at 100 degreeC for 1 hour, toluene was removed and 49 g of solid products were obtained.
상기 생성물은 IR을 확인한 결과 하이드록시기 및 알릴기로부터 유래하는 흡수 피크를 갖지 않고, 하이드록시화 반응이 완결되어 있음이 알 수 있었다. 또, 1050㎝-1에 실록산 결합으로부터 유래하는 흡수 피크를 가지고 있었다. 또한, GPC에 의해 분자량을 측정한 결과 폴리스티렌 환산으로 중량 평균 분자량 26,000g/mol이었다.As a result of IR analysis, it was found that the product did not have absorption peaks derived from a hydroxy group and an allyl group, and that the hydroxylation reaction was completed. Moreover, it had an absorption peak derived from a siloxane bond at 1050 cm -1 . Further, as a result of measuring the molecular weight by GPC, the weight average molecular weight was 26,000 g/mol in terms of polystyrene.
[실시예 2] 피막형성용 조성물 및 피막의 제조[Example 2] Composition for film formation and preparation of film
실시예 1에서 제조된 실록산 수지 및 상기 실록산 수지 100중량부에 대하여 테트라메틸암모늄 3중량부를 부틸아세테이트 1리터에 첨가한 후 충분히 교반하여 혼합하고, 0℃에서 12시간 동안 숙성하여 피막형성용 조성물을 제조하였다. The siloxane resin prepared in Example 1 and 3 parts by weight of tetramethylammonium based on 100 parts by weight of the siloxane resin were added to 1 liter of butyl acetate, mixed with sufficient stirring, and aged at 0 ° C. for 12 hours to obtain a film-forming composition manufactured.
제조된 피막형성용 조성물을 실리콘 웨이퍼에 회전수 1000 rpm으로 도포한 결과, 두께 1.5㎛의 투명 박막을 형성하였다.As a result of applying the prepared film-forming composition to a silicon wafer at a rotation speed of 1000 rpm, a transparent thin film having a thickness of 1.5 μm was formed.
[실시예 3] 피막형성용 조성물 및 피막의 제조[Example 3] Composition for film formation and preparation of film
실시예 2에서 테트라메틸암모늄 대신 비스(4-t-부틸페닐이오도니움)트리플루오로메타네술포네이트를 사용한 것을 제외하고는 실시예 2와 동일하게 실시하여 피막을 형성하였다.A film was formed in the same manner as in Example 2, except that bis(4-t-butylphenyliodonium)trifluoromethanesulfonate was used instead of tetramethylammonium.
[실시예 4] 피막형성용 조성물 및 피막의 제조[Example 4] Preparation of film forming composition and film
실시예 2에서 실록산 수지 100중량부에 대하여 디펜타에리트리톨헥사아크릴 레이트 1중량부를 추가한 것을 제외하고는 실시예 2와 동일하게 실시하여 피막을 형성하였다.A film was formed in the same manner as in Example 2, except that 1 part by weight of dipentaerythritol hexaacrylate was added to 100 parts by weight of the siloxane resin in Example 2.
[실시예 5] 피막형성용 조성물 및 피막의 제조[Example 5] Composition for film formation and preparation of film
실시예 2에서 실록산 수지 100중량부에 대하여 디펜타에리트리톨헥사아크릴 레이트를 1중량부 및 광리다칼 발생제로 IRGACURE 184를 0.01중량부 추가한 것을 제외하고는 실시예 2와 동일하게 실시하여 피막을 형성하였다.In Example 2, the film was formed in the same manner as in Example 2, except that 1 part by weight of dipentaerythritol hexaacrylate and 0.01 part by weight of IRGACURE 184 as a photonic polycalcium generator were added with respect to 100 parts by weight of the siloxane resin. formed.
[비교예 1] 피막형성용 조성물 및 피막의 제조[Comparative Example 1] Preparation of film-forming composition and film
실시예 2에서 테트라메틸암모늄 3중량부를 사용하지 않은 것을 제외하고는 실시예 2와 동일하게 실시하여 피막을 형성하였다.A film was formed in the same manner as in Example 2, except that 3 parts by weight of tetramethylammonium was not used in Example 2.
[물성평가][Physical property evaluation]
실시예 2 내지 5에서 형성된 각각의 피막을 80, 120, 160, 200, 220℃의 온도로 15분간 경화한 후, 연필 경도 시험 및 PGMEA(Propylene Glycol Monomethyl ether Aectate)에 대한 내화학성을 테스트하여 아래 표 1에 나타내었다.After curing each of the films formed in Examples 2 to 5 at a temperature of 80, 120, 160, 200, and 220 ° C. for 15 minutes, a pencil hardness test and chemical resistance to PGMEA (Propylene Glycol Monomethyl ether Aectate) were tested, and the following Table 1 shows.
경화온도curing temperature
80℃80℃ 120℃120℃ 160℃160℃ 200℃200℃ 220℃220℃
실시예 2Example 2 연필경도pencil hardness 2H2H 3H3H 5H5H 5H5H 6H6H
내화학성chemical resistance 3232 7474 9393 9898 9999
실시예 3Example 3 연필경도pencil hardness 2H2H 2H2H 4H4H 4H4H 4H4H
내화학성chemical resistance 2828 6666 8585 9292 9595
실시예 4Example 4 연필경도pencil hardness 3H3H 3H3H 5H5H 6H6H 8H8H
내화학성chemical resistance 6868 8282 9191 9595 9696
실시예 5Example 5 연필경도pencil hardness 4H4H 4H4H 7H7H 9H9H 9H9H
내화학성chemical resistance 7272 8989 9797 9898 9898
비교예 1Comparative Example 1 연필경도pencil hardness 1H1H 1H1H 1H1H 1H1H 1H1H
내화학성chemical resistance 00 00 4646 6666 8888
특정한 실록산 수지 조성물과 열산 발생제 또는 열염기 발생제와의 조합을 포함하는 본 발명의 피막형성용 조성물로 경화된 피막이 높은 연필경도 및 내화학성을 가짐을 알 수 있다.It can be seen that the film cured with the film-forming composition of the present invention comprising a combination of a specific siloxane resin composition and a thermal acid generator or a thermal base generator has high pencil hardness and chemical resistance.
구체적으로 본 발명의 실시예 2 내지 5의 피막형성용 조성물로 제조된 피막이 열산 발생제 또는 열염기 발생제를 포함하지 않는 비교예 1의 피막형성용 조성물로 제조된 피막과 대비하여 보다 향상된 연필경도 및 내화학성을 가짐을 알 수 있다.Specifically, the pencil hardness of the film prepared from the film-forming composition of Examples 2 to 5 of the present invention is more improved compared to the film prepared from the film-forming composition of Comparative Example 1 that does not contain a thermal acid generator or a thermal base generator. And it can be seen that it has chemical resistance.
특히 열염기 발생제를 포함하는 본 발명의 실시예 2의 피막형성용 조성물로 제조된 피막이 열산 발생제를 포함하는 본 발명의 실시예 3의 피막형성용 조성물로 제조된 피막이 보다 향상된 물성을 가짐을 알 수 있다.In particular, the film made of the film-forming composition of Example 2 of the present invention containing a thermal acid generator has improved physical properties. Able to know.

Claims (10)

  1. 열산 발생제 또는 열염기 발생제; 및thermal acid generators or thermal base generators; and
    하기 화학식 1 및 화학식 2로 표시되는 반복단위를 포함하는 실록산 수지;를 포함하는 피막형성용 조성물. A composition for forming a film comprising a siloxane resin including repeating units represented by Formula 1 and Formula 2 below.
    [화학식 1] [Formula 1]
    Figure PCTKR2022013594-appb-img-000009
    Figure PCTKR2022013594-appb-img-000009
    [화학식 2][Formula 2]
    Figure PCTKR2022013594-appb-img-000010
    Figure PCTKR2022013594-appb-img-000010
    상기 화학식 1 및 화학식 2에서,In Formula 1 and Formula 2,
    R1 내지 R4는 서로 독립적으로 수소, (C1-C10)알킬 또는 (C1-C10)알콕시이며;R 1 to R 4 are each independently hydrogen, (C1-C10)alkyl or (C1-C10)alkoxy;
    R11 및 R12는 서로 독립적으로 (C1-C10)알킬이며,R 11 and R 12 are each independently (C1-C10)alkyl;
    R13 및 R14는 서로 독립적으로 (C6-C12)아릴이며;R 13 and R 14 are each independently (C6-C12)aryl;
    p 및 q는 서로 독립적으로 2 내지 10의 정수이며;p and q are independently of each other an integer from 2 to 10;
    s 및 t는 몰비로 0.5 ≤ s ≤1.0이며; t는 0 ≤ t ≤ 0.5이다.s and t are 0.5 ≤ s ≤ 1.0 in molar ratio; t is 0 ≤ t ≤ 0.5.
  2. 제 1항에 있어서,According to claim 1,
    상기 열산 발생제는 Bis(4-t-부틸페닐이오도니움)트리플루오로메타네술포네이트, 트리아릴술포니움헥사플루오로 안디모네이트, 트리아릴술포니움헥사플로오로포스페이트, 테트라메틸암모늄트리플루오로메타네술포네이트 및 트리 에틸암네플루오로술포네이트 중에서 선택되는 하나 또는 둘 이상이며;The thermal acid generator is Bis (4-t-butylphenyliodonium) trifluoromethanesulfonate, triarylsulfonium hexafluoroandimonate, triarylsulfonium hexafluorophosphate, tetramethylammonium one or two or more selected from trifluoromethanesulfonate and triethylamnefluorosulfonate;
    상기 열염기 발생제는 테트라메틸암모늄아세테이트, 테트라메틸암모늄옥틸레이트, 테트라부틸암모늄아세테이트, 테트라부틸암모늄옥틸레이트, 트리메틸벤질암모늄아세테이트, 아자비시클로운데센포르메이트 (Azabicycloundeceneformate) 및 트리에틸아민p-톨루엔술포네이트 중에서 선택되는 하나 또는 둘 이상인 피막형성용 조성물.The thermobase generator is tetramethylammonium acetate, tetramethylammonium octylate, tetrabutylammonium acetate, tetrabutylammonium octylate, trimethylbenzylammonium acetate, azabicycloundeceneformate and triethylamine p-toluenesulfo One or two or more film-forming compositions selected from nates.
  3. 제 1항에 있어서,According to claim 1,
    상기 열산 발생제 또는 열염기 발생제는 실록산 수지 100중량부에 대하여 0.01 내지 10중량부 포함되는 피막형성용 조성물.The thermal acid generator or the thermal base generator is included in 0.01 to 10 parts by weight based on 100 parts by weight of the siloxane resin.
  4. 제 1항에 있어서,According to claim 1,
    상기 실록산 수지는 중량평균분자량이 5000 내지 100,000g/mol인 피막형성용 조성물.The siloxane resin is a composition for forming a film having a weight average molecular weight of 5000 to 100,000 g / mol.
  5. 제 1항에 있어서,According to claim 1,
    상기 화학식 1 및 2에서 R1 내지 R4는 수소 또는 (C1-C4)알킬이며; R11 및 R12는 서로 독립적으로 (C1-C4)알킬이며, R13 및 R14는 서로 독립적으로 또는 (C6-C10)아릴이며; p 및 q는 서로 독립적으로 2 내지 5의 정수인 피막형성용 조성물.In Formulas 1 and 2, R 1 to R 4 are hydrogen or (C1-C4)alkyl; R 11 and R 12 are each independently (C1-C4)alkyl, R 13 and R 14 are independently of each other or (C6-C10)aryl; p and q are independently of each other an integer of 2 to 5. A composition for forming a film.
  6. 제 1항에 있어서,According to claim 1,
    상기 피막형성용 조성물은 (메타)아크릴산에스테르가 더 첨가되는 피막형성용 조성물.The film-forming composition is a film-forming composition in which (meth)acrylic acid ester is further added.
  7. 제 6항에 있어서,According to claim 6,
    상기 (메타)아크릴산에스테르는 2가 이상 알코올의 (메타)아크릴산에스테르 또는 다관능 (메타)아크릴산 에스테르올리고머인 피막형성용 조성물.The (meth)acrylic acid ester is a (meth)acrylic acid ester of a dihydric or higher alcohol or a multifunctional (meth)acrylic acid ester oligomer.
  8. 제 1항에 있어서,According to claim 1,
    상기 피막형성용 조성물은 광라디칼발생제 또는 열라디칼발생제를 더 포함하는 피막형성용 조성물.The composition for forming a film further comprises an optical radical generator or a thermal radical generator.
  9. 제 1항에 있어서,According to claim 1,
    상기 피막형성용 조성물은 전자소자의 보호막 또는 절연막인 피막형성용 조성물. The film-forming composition is a film-forming composition that is a protective film or an insulating film of an electronic device.
  10. 제 1항 내지 제 9항에 선택되는 어느 한 항에 따른 피막용 조성물로 제조된 피막.A film made of the composition for a film according to any one of claims 1 to 9.
PCT/KR2022/013594 2021-09-13 2022-09-13 Composition for forming film, and film formed therefrom WO2023038488A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2021-0121827 2021-09-13
KR1020210121827A KR20230039014A (en) 2021-09-13 2021-09-13 A composition for forming a film and a film formed therefrom

Publications (1)

Publication Number Publication Date
WO2023038488A1 true WO2023038488A1 (en) 2023-03-16

Family

ID=85506790

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2022/013594 WO2023038488A1 (en) 2021-09-13 2022-09-13 Composition for forming film, and film formed therefrom

Country Status (2)

Country Link
KR (1) KR20230039014A (en)
WO (1) WO2023038488A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002088158A (en) * 2000-09-12 2002-03-27 Shin Etsu Chem Co Ltd Organosiloxane polymer, photocurable resin composition and method for forming pattern and film for protecting substrate
JP2003122005A (en) * 2001-10-09 2003-04-25 Shin Etsu Chem Co Ltd Photosetting resin composition, method for forming pattern, and film for protection of substrate
KR20130118450A (en) * 2012-04-20 2013-10-30 주식회사 아이에스엠 A photoactive compound including xanthene structure and an organic insulation layer composition comprising the same
KR20170029896A (en) * 2015-09-08 2017-03-16 모멘티브퍼포먼스머티리얼스코리아 주식회사 Organic siloxane-based polymer and photosensitive resin composition comprising the same
KR20170040470A (en) * 2015-10-05 2017-04-13 이창호 Curing composition for siloxane polymer and composition for transparent film comprising same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002088158A (en) * 2000-09-12 2002-03-27 Shin Etsu Chem Co Ltd Organosiloxane polymer, photocurable resin composition and method for forming pattern and film for protecting substrate
JP2003122005A (en) * 2001-10-09 2003-04-25 Shin Etsu Chem Co Ltd Photosetting resin composition, method for forming pattern, and film for protection of substrate
KR20130118450A (en) * 2012-04-20 2013-10-30 주식회사 아이에스엠 A photoactive compound including xanthene structure and an organic insulation layer composition comprising the same
KR20170029896A (en) * 2015-09-08 2017-03-16 모멘티브퍼포먼스머티리얼스코리아 주식회사 Organic siloxane-based polymer and photosensitive resin composition comprising the same
KR20170040470A (en) * 2015-10-05 2017-04-13 이창호 Curing composition for siloxane polymer and composition for transparent film comprising same

Also Published As

Publication number Publication date
KR20230039014A (en) 2023-03-21

Similar Documents

Publication Publication Date Title
EP1967540B1 (en) Curable composition
JP6171573B2 (en) Photosensitive resin composition and cured film
US20070099008A1 (en) Method of producing high molecular weight organopolysiloxane, composition comprising the high molecular weight organopolysiloxane, and optical semiconductor device sealed with cured product thereof
JP2015129288A (en) Polyhedron structure polysiloxane modification body and composition using the modification body
TWI848910B (en) Negative photosensitive resin composition and hardened film
JP6432075B2 (en) Photosensitive resin composition and cured film
WO2017039159A1 (en) Low temperature curing composition, cured film formed therefrom, and electronic device having cured film
WO2013094585A1 (en) Glass fiber composite resin substrate
WO2017155229A1 (en) Curable composition
KR20140138815A (en) Resin composition, transparent film for touch panel sensors using same, and touch panel
JP5103906B2 (en) Porous silica fine particles and method for producing the same
WO2014017795A1 (en) Complex sheet, method for manufacturing same, flexible substrate including same, and display device including same
WO2023038488A1 (en) Composition for forming film, and film formed therefrom
WO2012173459A2 (en) Composition having high refraction
WO2017195927A1 (en) Novel 2,4,6-triaminotriazine-based urethane acrylate compound and preparation method therefor
WO2022177332A1 (en) Photosensitive composition comprising organic metal compound and polysiloxane copolymer, and preparation method therefor
WO2014168393A1 (en) Negative type photosensitive organic-inorganic hybrid insulating film composition
WO2024143872A1 (en) Coating composition containing silsesquioxane polymer, and flexible display film
WO2018088713A1 (en) Curable composition
WO2010140804A2 (en) Norbornene resins for encapsulating optical device
CN116063637B (en) Composition for forming dielectric film, application thereof and display device
JP5571342B2 (en) Polysiloxane composition, cured product obtained therefrom, and insulating film
KR102613806B1 (en) UV moisture hybrid curable polysiloxane composition, polysiloxane cured film prepared therefrom, and uses thereof
WO2014088180A1 (en) Adhesive composition for solar cell module, adhesive member for solar cell module formed therefrom, and solar cell module comprising same
CN116063925B (en) Photocurable composition, hard coating layer thereof and application thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22867756

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22867756

Country of ref document: EP

Kind code of ref document: A1