WO2015105379A1

WO2015105379A1 - Novel novolac hardener having alkoxysilyl group, method for preparing same, composition containing same, hardened product, and use thereof

Info

Publication number: WO2015105379A1
Application number: PCT/KR2015/000243
Authority: WO
Inventors: 전현애; 김윤주; 박수진; 박숙연; 탁상용; 박성환
Original assignee: 한국생산기술연구원
Priority date: 2014-01-09
Filing date: 2015-01-09
Publication date: 2015-07-16

Abstract

The present invention relates to a novolac hardener having an alkoxysilyl group, the novolac hardener exhibiting excellent heat resistance characteristics, such as a low coefficient of thermal expansion (CTE) and an increase in the glass transition temperature, when forming a composite; a method for preparing the same; a composition containing the same; a hardened product; and a use thereof. According to an embodiment of the present invention, provided are a novolac hardener having an alkoxysilyl group of chemical formulas I-1 to I-4; a method for preparing the novolac hardener having an alkoxysilyl group of chemical formulas I-1 to I-4 through alkenylation and alkoxysilylation of the novolac hardener; a method for preparing the novolac hardener having an alkoxysilyl group of chemical formulas I-1 to I-4 through alkoxysilylation of the novolac hardener; a composition containing the novolac hardener having an alkoxysilyl group of chemical formulas I-1 to I-4; a hardened product thereof; and a use thereof. A composite comprising the novel hardener having an alkoxysilyl group according to the present invention exhibits a low CTE and a high glass transition temperature through a chemical bond between the alkoxysilyl group of the hardener and a phenol or epoxide group as well as a chemical bond between the alkoxysilyl group of the hardener and a filler.

Description

【Specification】

[Name of invention]

New novolac curing agents having alkoxysilyl groups, preparation methods thereof, compositions comprising the same, cured products and uses thereof

Technical Field

example. The present invention is a novel novolac curing agent having an alkoxysilyl group exhibiting excellent heat resistance in the composite (hereinafter also referred to as 'new novolac curing agent' or 'novolak curing agent of the present invention'), a method for preparing the same, a composition comprising the same, It relates to a cured product thereof and its use. More specifically, the present invention has in the composite _material, an excellent heat resistance, specifically, the low thermal expansion characteristics, (also which includes a Tg less does not exhibit a glass transition temperature) Glass jeonyieun lift, and a group, alkoxysilyl group that exhibits good flame retardant New novolac curing agents, methods for preparing the same, compositions comprising the same, cured products thereof and uses thereof.

[Technological Background of the Invention] ^' -The thermal expansion coefficient of epoxy resin is about 50 ~ 80 ppm / ° C, and the thermal expansion coefficient of ceramic material and metal material which are inorganic particles (for example, the thermal expansion coefficient of silicon is 3 ~ 5 ppm / ^° C, the thermal expansion coefficient of copper is 17ppm / ^° C.) The coefficient of thermal expansion is very large, several times to several ten times. Thus, for example, when the epoxy resin is used together with an inorganic material or a metal material in the semiconductor, display field, etc., The coefficient of thermal expansion significantly limits the design and processing of parts. In addition, for example, in the case of semiconductor packaging in which a silicon wafer and an epoxy substrate are used adjacent to each other, or when an inorganic barrier film is coated on a polymer film to impart gas barrier properties, the difference in coefficient of thermal expansion between materials ( CTE (mismatch) causes product defects such as inorganic layer cracking, substrate warpage, peeling off coatings, and substrate breakage. Due to the large CTE of this epoxy resin and the resulting dimensional change, next-generation semiconductor substrates, printed circuit boards (PCBs), packaging, OTFK Organic Thin Film Transistors, and flexible display substrates Technology development, etc.) is limited. Specifically, in the semiconductor and PCB field, due to the epoxy having a very high CTE compared to the metal / ceramic material, it is difficult to design the next-generation components that require high integration, high fineness, flexibility, and high performance. . To improve the thermal expansion properties (ie small coefficient of thermal expansion) of epoxy resins to date, new epoxy resins generally have (1) complexing epoxy resins with inorganic particles (inorganic fillers) and / or glass fibers or (2) reduced CTEs. A method of designing has been used. In order to improve the thermal expansion properties, inorganic particles as epoxy resin and filler In the case of complexation, the use of a large amount of non-subsidiary silica particles of about 2-30 卿 size can reduce CTE. However, there is a problem in that workability is degraded due to the filling of a large amount of inorganic particles. That is, problems such as reduced fluidity due to a large amount of inorganic particles and void formation during narrow filling may occur. In addition, the CTE of the epoxy composite including glass fibers is greatly reduced, but still shows a high CTE compared to silicon chips. As described above, due to the limitations of the current epoxy composite technology, the production of highly integrated high performance electronic components such as next-generation semiconductor substrates and PCBs is limited. Therefore, there is a need for the development of epoxy composites with improved thermal expansion properties, ie, low CTE and high glass transition properties, to overcome problems such as high CTE and the resulting heat resistance and lack of processability.

[Content of invention]

Problem to be solved

According to the present ⁱ to name one embodiment, the improved heat resistance in the composite material, specifically, there is provided a new novolak curing agent having an alkoxysilyl group representing a low CTE and a high glass transition temperature and excellent flame retardancy. According to another embodiment of the invention, the improved composites specifically low CTE, high glass transition temperature and good flame retardancy A method for producing a new novolac curing agent having an alkoxysilyl group is provided.

According to another embodiment of the present invention, there is provided a composition comprising a new novolac curing agent having an alkoxysilyl group which exhibits improved heat resistance in the composite, specifically low CTE, high glass transition temperature and good flame retardancy.

Furthermore, according to another embodiment of the present invention, there is provided a cured product of a composition comprising a new novolac curing agent having an alkoxysilyl group exhibiting improved heat resistance properties, in particular low CTE, high glass transition temperature and excellent flame retardancy in the composite. ᅳ

Moreover, according to another embodiment of this invention, the use of the composition containing the new novolak hardening | curing agent which has an alkoxylsilyl group by one embodiment of this invention is provided.

[Measures of problem]

According to the first aspect, there is provided a novolak curing agent having at least one alkoxysilyl group selected from the group consisting of the following formulas (1-1) to (1-4). [Formula 1-1]

(In Chemical Formula 1-1, Z is one of the groups consisting of the following Chemical Formulas 1A to 1F.

[Formula 1-3]

[Formula 1-4]

(In the above formula 1-4 p is 1 or ^2,

X-cr

And

R is a C1-C10 straight or branched alkyl group. )

(In Chemical Formula I ′ 1 to 1-4, At least one A is of formula A2 or A3, if at least one is A2, the remaining A is of formula B2 or hydrogen, if at least one is A3, the remaining A is hydrogen, and n is an integer of at least 1 . )

[Formula A2]

-(CH ₂ ) _m -SiRi ₂ R ₃

[Formula A3]

-CONH (CH ₂ ) _m -SiRiR ₂ R ₃

(In the formulas A2 and A3, at least one of to R ₃ is a straight or branched chain alkoxy group having 1 to 5 carbon atoms, the remainder is a straight chain black or branched alkyl group having 1 to 10 carbon atoms, m is an integer of 3 to 10 to be. )

[Formula B2]

-(CH ₂ ) rCH = CH ₂

(Formula, 1 is an integer from 1 to 8.) According to the second aspect, the starting material of any one of the formulas (IA-1 to IA-4) and the alkenyl compound of the formula (Π) in the presence of a base and an optional solvent To form an intermediate of any one of the following Formulas IB ′ 1 to IB-4; And a platinum catalyst-and any one of formulas IB-1 to IB-4 above in the presence of any solvent. A second step of reacting an intermediate with an alkoxysilane of the formula (II) to form a compound of formula (I) 1 to compound (IV) having a structure of formula (A2); Provided is a method for producing a novolac curing agent having any one alkoxysilyl group selected from the group consisting of:

[Formula IA ᅳ 1]

(In the above formula (IA-1), X is one group group consisting of the following formulas 2A to 2F.

[Formula IA-2]

[Formula IA-3]

[Formula I.A ᅳ 4]

(In formula IA-4, p is 1 or 2 and xl is

And

, R is a C1-C10 straight or branched alkyl group. (In Formulas IA-1 to IA-4, n is an integer of 1 or more.)

[Formula IB-1]

(Wherein Π is one of the groups consisting of the following chemical marks 3A to 3F)

[Formula IB-2]

[Formula IB-3]

In which R is a C1-C10 linear or branched alkyl group.) (In Formulas IB— 1 to IB-4, at least one D may be represented by Formula B2, and the remainder may be hydrogen. N is an integer of 1 or more. to be.)

[Formula B2]

(Wherein 1 is an integer from 1 to 8).

[Formula Π]

X- (CH ₂ ) rCH = CH ₂

(Wherein 1 is an integer of 1 to 8, X is CI, Br, I,-S0 ₂ ᅳ CH ₃ ,-S0 ₂ _CF ₃ , or -0-S0 ₂ -C ₆ — CH ₃ )

[Formula fflA]

HSiR _a R _b Rc

(In the above formula, at least one of R _a to R _c is a straight chain or molecular chain C1-C5 alkoxy group, and the rest is a straight chain black branched CI—C10 alkyl group.)

[Formula 1-2]

[Formula I ᅳ 3]

[Formula 1-4]

(In Formula 1-4, p is 1 or 2,

X is

And

Where R is a C1-C10 straight or branched alkyl group.)

(In Formulas 1-1 to 1-4, at least one A is Formula A2 _{: the} remainder is Formula B2 or hydrogen, and n is an integer of 1 or more.) [Formula A2]

-(CH ₂ ) _m -SiRiR ₂ R ₃

(In Formula A2, at least one of R ₃ is a linear or branched alkoxy group having 1 to 5 carbon atoms, the remainder is a straight chain black or branched alkyl group having 1 to 10 carbon atoms, and m is an integer of 3 to 10. )

[Formula B2]

-(CH ₂ ), -CH = CH ₂

(Wherein 1 is an integer of 1 to 8.) According to the third aspect, in the second aspect, the first step corresponds to one equivalent of the hydroxy group of the starting material of one of Formulas IA-1 to IA-4. There is provided a process for producing a novolak curing agent having an alkoxysilyl group, which is carried out by reacting an alkylene group of the alkenyl compound of the formula [pi] to 0.01 to 10 equivalents. According to my fourth opinion. In a second aspect, the first step is a method for preparing a novolak curing agent having an alkoxysilyl group, which is performed by reacting for 120 hours at -20 ^° C to 100 ^° C for 1 hour. According to the fifth aspect, in the second aspect, the second step is an alkoxysilane equivalent to 1 equivalent of the alkenyl group of one of the intermediates of Formulas IB-1 to IB-4. There is provided a process for producing a novolac curing agent having an alkoxysilyl group, which is carried out by reacting to 0.1 equivalents to 5 equivalents. According to a sixth aspect, in the second aspect, the second step is a method for preparing a noblock curing agent having an alkoxysilyl group, which is carried out by reacting at 20 ° C. to 12 CTC for 1 to 72 hours. According to the seventh aspect, in the presence of an arbitrary base and an optional solvent, a starting material of any one of the following formulas IA-1 to IA-4 is reacted with an alkoxysilane of the following formula ΠΙΒ to have a structure of formula A3. Provided is a method of preparing a novolak curing agent having any one alkoxysilyl group selected from the group consisting of Formulas 1-1 to 1-4, comprising an alkoxysilylation step to form one of 1-4 compounds.

[Formula IA-1]

(In Formula (IA-1), X is one of the groups consisting of the following Formulas 2A to 2F.

[Formula IA-2]

[Formula IA-4]

(In Formula IA-4, p is 1 or 2,

(In the above formulas IA-1 to IA-4, n is an integer of 1 or more.)

[Formula ΠΒ]

0CN- (CH ₂ ) _m -SiRiR ₂ R ₃

(In the above formula (II), at least one of R 3 is a straight or branched chain alkoxy group having 1 to 5 carbon atoms, the rest is a straight or branched chain alkyl group having 1 to 10 carbon atoms, and m is an integer of 3 to 10.

 [Formula 1-3]

And

[Formula 1-4]

(In Formula 1-4, p is 1 or 2 and

X is

And

R is a C1-C10 straight or branched alkyl group

(In the above formulas I '1 to 1-4, at least one A is the following formula A3, the remainder is hydrogen, and n is an integer of 1 or more.) [Formula A3]

-C0NH (CH ₂ ) _n rSiRiR ₂ R 3

(In Formula A3, at least one of ¾ is a linear black alkoxy branched alkoxy group having 1 to 5 carbon atoms, the remainder is a straight or branched chain alkyl group having 1 to 10 carbon atoms, and m is an integer of 3 to 10.) According to the eighth aspect, in the seventh aspect, the alkoxysilylation step is performed so that the alkoxysilane is 0.1 to 5 equivalents to 1 equivalent of the hydroxy group of the starting material of one of Formulas I A-1 to IA-4. the production method of the novolac curing agent having an ^"alkoxysilyl group provided that banung was performed. According to a ninth aspect, in the seventh aspect, the alkoxysilylation step provides a method for preparing a novolac curing agent having an alkoxysilyl group, which is performed by reacting ^at -20 ^° C to 120 ^° C for 1 to 72 hours. According to a tenth aspect, there is provided a composition comprising an epoxy resin and a novolac curing agent having at least one alkoxysilyl group selected from the group consisting of the following formulas 1-1 to 1-4.

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

(In Formula 1-4, p is 1 or 2,

X is

And

R is a straight or branched chain alkyl group of Cl-ClO.)

(In the above formula 1-1 to 1-4,

At least one A is of formula A2 or A3 and at least one is A2 Remaining A is the following formula B2 or hydrogen, when at least one is A3, the remaining A is hydrogen, n is an integer of 1 or more. )

Formula A2.

-(CH ₂ ) _m -SiRiR ₂ R ₃

[Formula A3]

-C0NH (CH ₂ ) _m -Si i ₂ R 3

(In Formulas A2 and A3, at least one of to R ₃ is a straight or branched chain alkoxy group having 1 to 5 carbon atoms, the rest is a straight or branched chain alkyl group having 1 to 10 carbon atoms, and m is an integer of 3 to 10. .)

[Formula B2]

-(CH ₂ ), -CH = CH ₂

(In formula, 1 is an integer of 1-8.) According to the eleventh aspect, in the tenth aspect, the epoxy resin is a glycidyl ether epoxy resin, glycidyl epoxy resin, glycidylamine epoxy resin And at least one composition selected from the group consisting of glycidyl ester epoxy resins. According to a twelfth aspect, in the eleventh aspect, the epoxy resin has a core structure of bisphenol, biphenyl, naphthalene, benzene, thiodiphenol, fluorene, anthracene, isocyanurate, and triphenylmethane. A composition having 1,1,2,2-tetraphenylethane, tetraphenylmethane, 4,4'-diaminodiphenylmethane, aminophenol, alicyclic, aliphatic, or novolak unit is provided. According to the thirteenth aspect, in the eleventh or twelfth aspect, the epoxy resin is provided with a composition comprising an epoxy resin with or without an alkoxysilyl group. According to the fourteenth aspect, in the tenth aspect, a composition further comprising inorganic particles or / and fibers as a filler is provided. According to a fifteenth aspect, in the fourteenth aspect, the inorganic particles are at least one composition selected from the group consisting of silica, zirconia, titania, alumina, silicon nitride, aluminum nitride, and silsesquioxane. According to the sixteenth aspect, in the fourteenth aspect, the inorganic particles are provided with a composition containing 5 wt% to 95% based on the total weight of solids of the composition. According to a seventeenth aspect, in the sixteenth aspect, the inorganic particles A composition is provided that includes 30 wt% to 95% based on the total weight of solids. According to the eighteenth aspect, in the sixteenth aspect, the inorganic particles are provided in a range of 5 wt% to 6 (½ «based on the total weight of solids of the composition. According to the nineteenth aspect, in the fourteenth aspect The fiber is glass fiber selected from the group consisting of E glass fiber, T glass fiber, S glass fiber, NE glass fiber, H glass fiber, and quartz; and liquid crystal polyester fiber, polyethylene terephthalate fiber, wholly aromatic fiber, polybenzoxazole fiber, nylon fiber, polyethylene naphthalate fiber, polypropylene fiber, polyethersulfone fiber, polyvinylidene fluoride fiber, polyethylene sulfide fibers, ^■ and a polyether selected from the group consisting of ketone fiber At least one composition selected from the group consisting of organic fibers is provided. In the 19th aspect, the fiber was provided with the composition which is E glass fiber .. According to the 21st aspect, the composition is the T glass fiber in 19th aspect. In terms of the fiber is the composition A composition is provided which comprises from 10 wt% to 90 ¾ with respect to the total weight of solids. According to the twenty third aspect, when the fiber is included as the filler according to the fourteenth aspect, a composition further comprising inorganic particles is provided. According to the twenty-fourth aspect, in the tenth aspect, a composition further comprising an alkoxysilyl group semi-aqueous catalyst is provided. According to a twenty-fifth aspect, in the twenty-fourth aspect, the alkoxysilyl group reaction catalyst is selected from nitric acid, sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, ammonia, K0H, NH ₄ 0H, amine, transition metal alkoxide, and tin (t in) compound. At least one composition selected from the group consisting of is provided. According to a twenty sixth aspect, in the twenty fourth aspect, the composition is provided in which the semi-aqueous catalyst is contained in an amount of 0.01 phr to 10 phr relative to the epoxy resin having an alkoxysilyl group. According to a twenty seventh aspect, in the twenty fourth aspect, a composition further comprising water is provided. According to the 28th aspect, the electronic material containing the composition in any one of 10th-27th aspect is provided. According to the 29th opinion, the 10th to 27th opinions

Provided is a substrate comprising. According to the thirtieth opinion, tenth to twenty-seventh opinion

A film comprising is provided. According to the thirty-first aspect, there is provided a laminate comprising a metal worm on a base layer made of the composition of any one of the tenth to twenty-seventh aspects. According to the thirty-second aspect, in the thirty-first aspect, a printed wiring board including a laminated board is provided. According to the thirty-third aspect, in the thirty-second aspect, a semiconductor device including a printed wiring board is provided. According to a thirty-fourth aspect, there is provided a semiconductor packaging material comprising the composition of any one of the tenth to twenty-seventh aspects. According to the thirty fifth aspect, in the thirty-fourth aspect, a semiconductor device including a semiconductor packaging material is provided. According to a thirty sixth aspect, there is provided an adhesive comprising the composition of any one of the tenth to twenty seventh aspects. According to a thirty seventh aspect, there is provided a paint comprising the composition of any one of the crabs 10 to 27. According to a thirty eighth aspect, there is provided a composite material comprising the composition of any one of the tenth to twenty seventh aspects. According to a thirty-ninth aspect, there is provided a prepreg comprising the composition of any one of the tenth to twenty-seventh symptoms. According to the 40th aspect, in the 39th aspect, the laminated board with a metal layer arrange | positioned at the prepreg is provided. According to a forty-first aspect, the cured product of any one of the tenth to twenty-seventh symptom compositions is provided. According to the forty-fourth aspect, in the forty-first aspect, a cured product of the composition having a thermal expansion coefficient of 60 ppm / ^° C. or less is provided. 43 According to the aspect ^", 41st aspect the cured product of the composition the glass transition temperature does not represent a higher or a glass transition temperature greater than 100 ^° C is provided in the.

【Effects of the Invention】

The composition comprising a new novolac curing agent having an alkoxysilyl group according to the present invention is used in the composite and / or cured product to form an interfacial bond between an alkoxysilyl group and a filler (fibers and / or inorganic particles) and to react an alkoxysilyl group with an epoxy and a curing agent. The formation of further chemical bonds by means of improved heat resistance. That is, the CTE of the epoxy composite is reduced and the glass transition degree is increased or the glass transition temperature is not exhibited (hereinafter referred to as 'Tg lease'). Furthermore, the hardened | cured material of the composition containing the novolak hardening | curing agent which has the alkoxy silyl group by this invention shows the outstanding flame retardance by introduction of the alkoxy silyl group. In addition, the novel novolak curing agent having an alkoxysilyl group according to the present invention is easy to be solidified (sol id) to an epoxy resin having an alkoxysilyl group, so that it is easy to be applied to a process requiring a solid phase sample, and brittleness of the cured product. (br it leness) and adhesion are improved. Furthermore, in the case of applying the composition according to the present invention to a metal film of a substrate, the chemical film of the functional group on the surface of the metal film and the alkoxysilyl group is applied to the metal film. Excellent adhesion.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a result of measuring the length change with the temperature of the glass fiber composite body by Example 1 and the comparative example 1. FIG.

[Specific contents to carry out invention]

The present invention has improved heat resistance properties when forming a composite using a composition comprising a curing agent having an alkoxysilyl group, specifically having a low CTE and a high Tg (including Tg lease) and / or having an alkoxysilyl group having excellent flame retardancy in the cured product. It is to provide a new novolac curing agent, a method for preparing the same, a curing agent composition and a cured product comprising the same, and uses thereof. In the present invention, "composite or epoxy composite" refers to a cured product of a composition comprising an epoxy resin curing agent and a filler (fibers and / or inorganic particles). As used herein, the term "cured or epoxy cured product" refers to a cured product of a composition comprising an epoxy resin and a curing agent. In addition to the epoxy resin and the curing agent, fillers, optional additional curing agents, optional curing catalysts, and other additives Comprising at least one selected from the group consisting of. The hardened | cured material of a composition is said. In addition, the cured product may include a semi-cargo. In general, inorganic particles And / or a cured product reinforced with fibers, so that the cured product has a broader meaning than the composite, but an inorganic particle. And / or a cured product reinforced with fibers may be understood to have the same meaning as the composite.

-The new novolac curing agent according to the present invention forms an interfacial bond with the surface of the filler (fibers and / or inorganic particles) and / or an alkoxysilyl group, an epoxide group and a phenol group and a chemical bond when the complex is formed by curing. Therefore, it shows low CTE and high glass transition temperature synergistic effect or Tg-less (less). Therefore, the dimensional stability is improved. In addition, the cured product including the novolac curing agent according to the present invention exhibits excellent flame retardancy. Furthermore, the composition according to the present invention is applied to a chemically treated metal film, for example, copper foil, and the like, and the alkoxysilyl group of the curing agent is applied to the metal surface. As it is chemically bonded with -0H group on the metal surface by treatment, it shows excellent adhesion with metal film.

1. Novolac curing agent having an alkoxysilyl group

According to one embodiment of the present invention, there is provided a novolak curing agent having any one alkoxysilyl group selected from the group consisting of the following formulas I '1 to 1-4. [Formula I ᅳ 1]

In Chemical Formula I ′ 1, Z is one of the groups consisting of the following Chemical Formulas 1A to 1F.

1A 1B 1C

Formula I 一 3

[Formula 1-4]

In formula I 4, p is 1 or 2

CH _r ,

X is

And

R is a straight or branched alkyl group of CI—CIO.)

In Chemical Formulas 1-1 to 1-4, At least one of the plurality of A is of formula A2 or A3; At least when one of A2, and when the remaining A are hydrogen or the formula B2, at least one of which is A3, and the remaining A are _hydrogen.

n is 1 or more, for example, the integer of 1-1000.

[Formula A2]

-(CH ₂ ) _m -S iR ₁ R ₂ R ₃

[Formula A3]

In Chemical Formulas A2 and A3, at least one of R ₃ and R ₃ is an alkoxy group having 1 to 5 carbon atoms, preferably an alkoxy group having ₃ to ₃ carbon atoms. More preferably, it is a methoxy group or a special group. The remainder is a C1-C10 alkyl group, m is an integer of 3-10, Preferably it is an integer of 3-6. The alkoxy group and the alkyl group may be straight chain black or branched chain.

[Formula B2]

(Wherein 1 is an integer of 1 to 8) In the novolak curing agent having an alkoxysilyl group according to an embodiment of the present invention, ^"In formulas A2 and A3, preferably at least one of the alkoxy groups of from ¾ to methoxy is preferable in terms of improving the reactivity, and Preference is given to the semi- stable stability, i.e., in terms of sample stability and / or good reactivity.In this specification, an "alkoxy group" is a monovalent group which is —OR (R is an alkyl group), which may be linear or branched, In this specification, the branched chain and the branched chain may be used interchangeably. In this specification, an "alkyl group" refers to a monovalent ent hydrocarbon group, which may be linear or branched, and preferably 1 It has a carbon number of 10 to 10, More preferably, it has a carbon number of 1 to 5. Furthermore, the alkoxysilyl group by one Embodiment of the said invention is mentioned. The novolac curing agent having exhibits low CTE and high glass transition temperature or Tg-less when forming a composite of the composition comprising the same.

2. Method for producing a novolac curing agent having an alkoxysilyl group

The novolac curing agent having an alkoxysilyl group represented by Chemical Formulas 1-1 to 1-4 according to one embodiment of the present invention may be synthesized by the following method. The manufacturing method of the novolak hardening agent which has an alkoxy silyl group mentioned later is simple and simple compared with the manufacturing method of the epoxy resin which has an alkoxy silyl group.

(1) Process for preparing a nobulac curing agent having an alkoxysilyl group of formulas 1-1 to 1-4 having formula A2 (Method 1) According to another embodiment of the present invention, formulas 1-1 to 1 having a substituent of formula A2 Provided are a method for producing a new novolac curing agent of 1-4. New novolac curing agents with substituents of formula A2 can be prepared by the process by alkenylation (first step) and alkoxysilylation (second step) of the starting materials. In the first step, a reaction of a hydroxy group in the starting material by reaction of a starting material of one of the following formulas IA-1 to ΙΑ-4 (hereinafter, also referred to as 'starting material' or 'starting material IA') and alkenyl of the formula At least one of the alkenylated intermediates of any one of formulas IB ′ 1 to IB-4 (hereinafter referred to as “intermediate IB”).

[Formula IA-1]

X in Formula IA ′ 1 is one of a group consisting of Formulas 2A to 2F.

 [Formula IA-4]

xl is

, R is a C1-C10 linear or branched alkyl group. In Formulas IA-1 to IA-4, n is an integer of 1 or more. Specifically, in Formulas IA-1 to IA-4, n is an integer of 1 or more, for example, an integer of 1 to 1000, which includes all integers in these ranges and any other smaller range of integers. It means. In formula (IA-4), p is 1 or 2.

[Formula IB-1]

In the formula, Π is selected from the group consisting of the following formulas 3A to 3F One.

[Formula IB-4]

X2 in Formula IB-4

R is a C1-C10 linear or branched alkyl group. )

In Formulas IB-1 to IB-4, at least one of a plurality of D may be represented by Formula B2, and the rest may be hydrogen.

n is an integer of 1 or more.

In formula IB-4, p is 1 or 2.

[Formula B2]

-(CH ₂ ) rCH = CH ₂

In formula, 1 is an integer of 1-8, Preferably it is an integer of 1-4. [Formula Π]

X- (CH ₂ ) rCH = CH ₂

Wherein 1 is an integer of 1 to 8, preferably an integer of 1 to 4, X is a halide such as CI, Br or I, -O S0 ₂ -CH ₃ , -0 一 S0 ₂ -CF ₃ , Or S S0 ₂ ᅳ C ₆ H ₄ -CH ₃ . Alkenylation, the reaction of the first step, is carried out by reacting the starting material of one of the above formulas IA-1 to IA-4 with the alkenyl compound of the formula Π, which reaction is carried out in the presence of a base and an optional solvent. For example, the starting material and the alkenyl compound may be reacted in the presence of a base and an optional solvent such that the alkenyl compound corresponds to 1 equivalent of the hydroxy group of the starting material and the alkenyl group is from 0.1 to 10 equivalents. Get IB The reaction product is reacted with a stoichiometric equivalence ratio, and in consideration of this, the reaction product is reacted with the equivalence ratio to obtain a desired intermediate product IB. The reaction temperature and reaction time of the first step reaction are dependent on the type of reactant, but, for example, the intermediate product IB is obtained by reacting the reaction at 20 ^° C. to 100 ^° C. for 1 hour to 120 hours. Examples of bases that can be used include, but are not limited to, for example, KOH, NaOH, ₂ C0 ₃ , Na ₂ C0 ₃ , KHC0 ₃ , NaHC0 ₃₎ NaH, triethylamine, diisopropylethyl Amines. These bases may be used alone or in combination of two or more of them. The base may be used in an amount of 0.01 to 5 equivalents based on 1 equivalent of the hydroxy group of the starting material IA in terms of reaction efficiency. In the first stage reaction, the solvent may optionally be used as necessary. For example, the solvent may not be used if the viscosity of the reactants at the reaction temperature is suitable for the reaction to proceed without reaction in the first step reaction. That is, mixing and stirring with the reactants may proceed smoothly without solvent. If the viscosity of the reaction product is low enough, it does not require a separate solvent, which can be easily determined by those skilled in the art. In the case of using a solvent, as a possible solvent, the reaction product can be dissolved well, and any organic solvent can be used as long as it can be easily removed after the reaction without adversely affecting the reaction. For example, acetonitrile, tetrahydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formamicle (DMF), dimethyl sul foxide (DMMS0), methylene chloride (MC), ¾0, alcohols and roluene can be used. have. These solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited and may be used in a suitable amount and / or concentration in a range in which the reaction product is sufficiently dissolved and does not adversely affect the reaction. Those skilled in the art can make appropriate selections in view of this. Then, in the second step, the intermediate product IB is obtained by alkoxysilylation. The novolak hardening | curing agent of Formula 1-1 to 1-4 which has substituent A2 by one embodiment of the invention is obtained. This reaction can be carried out in the presence of a catalyst and any solvent, in which case a platinum catalyst is preferred. In the second stage reaction. Since the intermediate product IB and the alkoxysilane react at an equivalence ratio of the alkenyl group and the alkoxysilane of the intermediate product IB according to the stoichiometry, in consideration of this, the alkoxysilane of the general formula ΙΠΑ is 0 to 1 equivalent of the alkenyl group of the intermediate product IB. Intermediate IB is reacted with an alkoxysilane of the formula

[Formula ΙΠΑ]

HSiR _a R _b R _c

In the above formula mA, at least one of R _a to R _c is a C1-C5 alkoxy group, preferably a C1-C3 alkoxy group, more preferably a mesophilic or ethoxy group and the remainder is an α-αο alkyl group, the alkoxy group And the alkyl group may be straight chain black branched chain. The reaction temperature and reaction time of the second stage reaction vary depending on the reactant, but for example, a novolak curing agent of the formulas 1-1 to 1-4 having a substituent A2 by reacting for 1 hour to 72 hours at 2CTC to 120 ° C. Is obtained. The platinum catalyst that can be used in the second reaction reaction is not limited thereto. For example, a platinum catalyst of Pt¾ or H ₂ PtCl ₆ (CMoroplat inc c acid) may be used. The platinum catalyst is preferably used in an amount of lxlO— ⁴ to 0.05 equivalents based on 1 equivalent of the alkenyl group of the intermediate product IB in terms of reaction efficiency. The solvent in the second stage reaction can optionally be used as needed. For example, a separate water banung viscosity at the reaction temperature without a solvent, in the ^"second reaction step suitable for the reaction proceeds may not use a solvent. That is, if the viscosity of the reaction product is low enough that the mixing and stirring of the reaction product can proceed smoothly without a solvent, a separate solvent is not required, which can be easily determined by those skilled in the art. In the case of using a solvent, as a possible solvent, the reaction product can be dissolved well, and any aprotic solvent can be used as long as it can be easily removed after the reaction without any adverse effect on the reaction. For example, but not limited to, toluene, acetonitrile, tetrahydrofuran (THF), methyl ethyl ketone (Μ), dimethyl formamide (DMF), dimethyl sul foxide (DMSO), methylene chloride (MC), and the like Can be used. These solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, and may be used in a suitable amount and / or concentration within a range in which the reactants are sufficiently dissolved and do not adversely affect the reaction, and those skilled in the art may select appropriately in consideration of this. have. An exemplary reaction method of the above-described preparation method (1) of Formula 1-1, wherein Z is IA, is as follows.

As defined in the novolac curing agent of Formulas 1-1 to 1-4, at least one of the plurality of substituents A of Formulas 1-1 to 1-4 is a structure of Formula A2 (ie, an alkoxysilyl group), and the rest May be hydrogen. The number of alkoxysilyl groups in the formula (1-1) to (1-4) is the first of the reaction 1 In the step, the equivalence and reaction of the alkenyl compound can be varied by controlling the number of hydroxy groups to be alkenylated by controlling the degree. This can be appropriately adjusted by those skilled in the art in view of the reaction from the above disclosure.

(2) Process for preparing a novolac curing agent having alkoxysilyl groups of formulas 1-1 to 1-4 having a substituent of formula A3 (Method 2) According to another embodiment of the present invention, formula (1) having a substituent of formula (A3) A method for producing a novolac curing agent of -1 to I14 is provided. The novolac curing agents of formulas 1-1 to 1-4 with substituents of formula A3 may be prepared by an alkoxysilylation step that alkoxysilylates the starting material. In the alkoxysilylation step, the starting material is an alkoxysilylation of one of the formulas IA-1 to IA-4 to obtain a novolak curing agent of one of formulas 1-1 to 1-4 having a substituent of formula A3. On the other hand, the alkoxysilylation step may be carried out in the presence of any base and any solvent. In the alkoxysilylation step, the alkoxysilane having the isocyanate functional group of the starting material IA and the following formula ΠΙΒ is 0.1 to 5 equivalents of the alkoxysilane having the isocyanate functional group of the formula ΠΙΒ relative to 1 equivalent of the hydroxy group of the starting material IA. Lee Dodoktok-from 20 ° C to 120 ° C for 1 to 72 hours Please reply.

[Formula mB]

0CN- (CH ₂ ) _ni- SiRiR ₂ R _{3 In the} above formula (ΙΠΒ), at least one of to is an alkoxy group having 1 to 5 carbon atoms, preferably an alkoxy group having 1 to 3 carbon atoms, more preferably a methoxy group or an hydroxy group to be. The hydroxy group is preferable in view of high reactivity, and the ethoxy value is preferable in view of sample stability and good reaction properties. The remainder is an alkyl group having 1 to 10 carbon atoms, wherein the alkoxy group and the alkyl group may be linear or branched, m is an integer of 3 to 10, preferably an integer of 3 to 6. In the alkoxysilylation step, the alkoxysilane having the starting material IA and the isocyanate functional group reacts with the hydroxy group of the starting material IA and the alkoxysilane in an equivalent ratio according to the stoichiometry, and thus taking into account the hydroxy group 1 of the starting material IA The alkoxysilane having the starting material IA and the isocyanate functional group is reacted such that the equivalent weight of the alkoxysilane is from 0.01 equivalents to 5 equivalents. The reaction temperature and reaction time of the alkoxysilylation step depend on the reaction water, but, for example, by reacting for 1 to 72 hours at 20 ° C. to 120 ° C. (A novolac curing agent of any one of formulas I ′ 1 to 1-4 having substituents of ΌΝΗ ((¾) _η − ^ ¾¾¾ is obtained.) The reaction of the alkoxysilylation step may be carried out in the presence of a base if necessary. The use of a separate base may result in a faster reaction reaction, but examples of the base that can be used include, but are not limited to, for example, K ₂ CO ₃ , Na ₂ CO ₃ , KHCOs, NaHC0 ₃ , triethylamine These bases may be used alone or in combination of two or more.In the case of using a base, the base is 0.1 to 1 equivalent of hydroxy group of the starting material IA. The use of equivalents to 5 equivalents is good in terms of reaction efficiency The solvent may be optionally used in the reaction of the alkoxysilylation step, for example, without the need for a separate solvent in the alkoxysilylation step. If the viscosity of the reactants in silver is suitable for the reaction to proceed, the solvent may not be used, i.e. if the viscosity of the reactants is low enough that the mixing and stirring of the reaction product can proceed smoothly without solvent, then no additional solvent is required. In the case of using a solvent, the possible solvent can dissolve the reaction product well, and any aproticity can be easily removed after the reaction without any adverse effect on the reaction. A solvent may be used, including but not limited to, for example, toluene, acetonitrile, tetrahydrofuran (THF), methyl ethyl ketone (MEK), dimethyl formaniide (DMF), DMS0 (dimethyl sul foxide), Methylene chloride (MC) and the like may be used. These solvents may be used alone or in combination of two or more black. The amount of the solvent used is not particularly limited and may be used in a suitable amount within a range in which the reaction product is sufficiently dissolved and does not adversely affect the reaction, and those skilled in the art may appropriately select it.

An exemplary reaction scheme of Reaction 2 of Formula 1-1 wherein Z is IA is as follows.

As defined in the novolac curing agents of Formulas 1-1 to 1-4, at least one of the plurality of substituents A of Formulas 1-1 to 1-4 is a structure of Formula A3 (ie, an alkoxysilyl group) and the rest is hydrogen Can be. The number of alkoxysilyl groups in Chemical Formulas 1-1 to 1-4 refers to the equivalent of alkoxysilane and reaction temperature in the alkoxysilylation step. It can be varied by controlling the number of hydroxy groups to be epoxidized by controlling. This can be appropriately adjusted by those skilled in the art in view of reactivity from the above disclosure.

3. Compositions Containing New Novolac Curing Agents

According to another embodiment of the present invention, there is provided a composition comprising an epoxy resin and at least one new novolac curing agent selected from the group consisting of the above formulas 1-1 to 1-4.

Any of the compositions provided in the present invention are used for electronic materials, for example, but not limited to, for example, semiconductor substrates such as IC substrates, build-up films, encapsulation materials (packaging materials), printed wiring boards, and the like. It can be used for various uses such as parts, adhesives, paints and composite materials. In addition, any composition provided in the present invention may be a curable composition comprising an inorganic material.

The composition according to any of the above and later embodiments of the present invention comprises as a curing agent at least one new novolac curing agent selected from the group consisting of Formulas 1—1 to 1-4 according to embodiments of the present invention. As such, it is understood that any kind and / or combination of compositions known in the art are included, and the epoxy resin constituting the composition, the curing agent of the present invention and conventional curing agents, curing accelerators (catalysts), inorganic materials (fillers) (Eg inorganic particles and / or Fiber) and other additives, and the mixing ratio is not limited. The epoxy resin may be any conventional epoxy resin known in the art, but is not particularly limited, for example, glycidyl ether-based epoxy resin, glycidyl-based epoxy resin, glycidylamine-based It may be at least one selected from the group consisting of an epoxy resin and a glycidyl ester epoxy resin. Further, the epoxy resin has a core structure of bisphenol, biphenyl, naphthalene, benzene, thiodiphenol, fluorene (fhiorene), anthracene, isocyanurate, triphenylmethane, 1,1,2,2-tetraphenyl Ethane, tetraphenylmethane, 4,4'-diaminodiphenyl methane, aminophenol alicyclic, aliphatic, or glycidyl ether epoxy resin having a novolak unit, glycidyl epoxy resin, glycidylamine epoxy At least one selected from the group consisting of a resin and a glycidyl ester epoxy resin. For example, the conventional epoxy resin is bisphenol, biphenyl, naphthalene, fluorene benzene, thiodiphenol, fluorene, anthracene as a core structure. Isocyanurate, triphenylmethane, 1,1,2,2-tetraphenylethane, tetraphenylmethane. 4,4 'ᅳ diaminodiphenylmethane, aminophenol, cycloaliphatic, aliphatic, or glycidyl ether epoxy resin having a novolak unit, glycidyl epoxy resin, glycidylamine epoxy resin, glycidyl It may be at least one selected from the group consisting of an ester epoxy resin. Furthermore, the existing and epoxy resins may or may not have an alkoxysilyl group. In the composition according to the above described and in some embodiments to be described later of the present invention, a curing agent as is "and includes the alkoxy silylated a novolac hardener, alkoxy silylated a novolac curing agents of the ^invention" of the present invention in addition to, the epoxy additionally Any conventional curing agent, generally known as a curing agent for resins, may be added, and as the existing curing agent, there is no particular limitation, for example, a novolac curing agent (a conventional novolak having no alkoxylsilyl group). Curing agents), amines, acid anhydrides and the like can be used. More specifically. Although not limited to this, as the amine curing agent, aliphatic amines, alicyclic amines, aromatic amines, other amines and modified polyamines can be used, and amine compounds containing two or more primary amine groups can be used. Specific examples of the amine curing agent include 4,4 'ᅳ dimethylaniline (diamino diphenyl methane) (4 _> 4'-Dimethylani 1 ine (di amino diphenyl methane, DAM or DDM), diamino diphenylsulfone (diamino di phenyl sul fone, DDS), m_ lung alkenylene di <min _(m -phenyl ene diamine) aromatic amine, at least one selected from the group consisting of diethylene triamine (dieihylene tri amine, DETA), diethylene tetraamine ( diethylene tetramine, tri iethy lene tetramine (TETA), m-xylene diamine (MXDA), methane diamine (MDA), Ν, Ν'- Diethylenediamine (N, N '-di et hy 1 ened i amine, Ν, Ν' -DEDA), tetraethylene pentaamine (TEPA), and hexamethy 1 ened i am i ne At least one aliphatic amine selected from the group consisting of: isophorone diamine (IPDI), N-aminoethyl pyrazine (AEP), bis (4 ᅳ amino 3-methylcyclonucleus) Other amines, polyamides, epoxides, such as one or more cycloaliphatic amines, dicyandiamides (DICY), etc. selected from the group consisting of methane (Bis (4-Aniino 3 ᅳ Methyl eye 1 ohexy 1) Methane, Larominc 260) Modified amines, such as a system, are mentioned. Examples of the phenol curing agent include, but are not limited to, phenol novolac resins, cresol novolac resins, bisphenol A novolac resins, xylene novolac resins, triphenyl novolac resins, biphenyl novolac resins and dicyclopentadiene novolacs. Resins, phenol P-xylene resins, phenol 4, 4'-dimethylbiphenylene resins, naphthalene phenol novolac resins and the like. Examples of acid anhydride-based curing agents include, but are not limited to, dodecenyl succinic anhydride (DDSA), aliphatic acid anhydrides such as poly azelaic poly anhydride, and nucleohydrophthalic anhydrides. Alicyclics such as hydrhydroph halic anhydride (HHPA), methyl tetrahydrophthalic anhydride (MeTHPA) and methylnadic anhydride (MNA) Anhydride, trimellitic not hydride (Trimellitic Anhydride, TMA), pyromellitic dianhydride hydride (pyromellitic acid di anhydr ide, PMDA), benzophenone tetracarboxylic carboxy acid dianhydride hydride ^{'(benzophenonetetracarboxyl} ic di anhydr i de, BTDA Aromatic acid anhydrides, such as a), tetrabromophthalic anhydride (TBPA), and halogen-based acid anhydride compounds such as chlorendic anhydride. In general, the degree of curing of the epoxy composite can be adjusted to the degree of reaction between the curing agent and the epoxy resin, and the content of the curing agent can be adjusted based on the concentration of the epoxy group of the epoxy resin according to the desired degree of curing. For example, when the curing agent of the present invention is used alone or in combination with an existing curing agent, the equivalent reaction of the curing agent and the epoxy group is such that the epoxy equivalent / curing agent equivalent ratio is 0.5 to 2.0, and, for example, It is preferable to adjust and use a hardening | curing agent so that it may become 0.8-1.5. Any curing agent that can be used to cure the epoxy resins not otherwise described herein also depends on the concentration of the total epoxy groups in the composition of the present invention depending on the desired degree of cure and based on the concentration of the epoxy functional groups and the semi-aromatic functional groups of the curing agent. Suitable amounts can be used in combination, as is common in the art.

Furthermore, according to one embodiment of the present invention, the above and later described of the present invention The composition comprising the new novolac curing agent according to any embodiment may further comprise an inorganic material (filler), for example inorganic particles and / or fibers, as needed, and for convenience the composition comprising the inorganic material " Composite compositions', as long as the composite composition comprises an epoxy resin, at least one new novolac curing agent and filler selected from the group consisting of Formulas 1-1 to 1-4. known any type and / or the combination is understood to include a composition, the epoxy resin constituting the composition, the curing agent of the present invention, a conventional curing agent, a curing accelerator (catalyst) which, _weapon material (filler) (e.g., Inorganic particles and / or fibers) and other additives are not limited to the type and compounding ratio. Any inorganic particles known to be used for reinforcement may be used, including but not limited to, consisting of silica (including, for example, fused silica and crystalline silica), zirconia, titania, alumina, silicon nitride and aluminum nitride At least one kind selected from the group consisting of at least one metal oxide selected from the group and silsesquioxane may be used, and the inorganic particles may be used alone or as a mixture with two or more kinds. In this case, it is preferable to use fused silica, although either crushed or spherical can be used. In order to raise the compounding quantity of a silica and to suppress the raise of the melt viscosity of a molding material, it is preferable to use a spherical thing. The inorganic particles are not limited thereto, but inorganic particles having a particle size of 0.5 nm to several tens (for example, 50 to 100) may be used in consideration of the use of the composite, specifically, the dispersibility of the inorganic particles. Can be. Since the inorganic particles are dispersed in the epoxy resin, the inorganic particles of the above sizes are preferably used together due to the difference in dispersibility according to the particle size. In addition, in order to raise the compounding quantity of an inorganic particle, it is preferable to mix | blend and make the particle | grain distribution of inorganic particle wider. In the composition comprising a new novolac curing agent and an epoxy resin according to an embodiment of the present invention, the inorganic particles may be suitably added to the epoxy resin according to the appropriate viscosity and use required for reducing and applying CTE of the epoxy composite. The content of the inorganic particles is based on the total weight of solids of the composition, while in the case of epoxy cured products, based on the total weight of the epoxy cured product, 5 wt% to 95 wt ¾, for example 5 wt% to 90 wt%, for example 10 wt% to 90wt¾>, for example 30 wt% to 95wt, for example 30wt% to 90wt%, for example 5 wt% to 60wt%, for example 10wt to 50%. More specifically, as an example, the composition of the present invention is a semiconductor encapsulant When used, this is not limitative, but considering the CTE value and the material processability, the content of the inorganic particles is, for example, relative to the total increase in the solid content of the composition, while in the case of epoxy cured products the total weight of the epoxy cured product. 30 wt% to 95 wt%, for example, 30 wt% to 90%. In addition, as an example, when the composition is used as a semiconductor substrate, the content of the inorganic particles in consideration of the CTE value and strength of the substrate, for example, relative to the weight of the total solids of the composition, on the other hand In the case of 5 wt% to 60 wt%, for example 10 wt% to 50%, based on the total weight of the epoxy cured product. On the other hand, when the fiber is used as an inorganic material, any kind and dimension of fiber generally used in the art may be used. The fiber is not limited thereto, and any fiber generally used for improving physical properties of the thermosetting resin and cured material may be used. Specifically glass fiber, organic fiber or a mixture of middles can be used. In addition, the term 'glass fiber' as used herein is used to mean not only glass fiber, but also glass fiber fabric, glass fiber nonwoven fabric, and the like. Although not limited to this, glass fibers include glass fibers such as E glass fiber, T glass fiber, S glass fiber, NE glass fiber, D glass fiber, quartz glass fiber, and the like. Or T glass fibers. Although it does not specifically limit as an organic fiber by this, Liquid crystalline polyester fiber, polyethylene terephthalate fiber, Selected from the group consisting of wholly aromatic fibers, polybenzoxazole fibers, nylon heart oil, polyethylene naphthalate fibers, polypropylene fibers, polyether sulfone fibers, polyvinylidene fluoride fibers, polyethylene sulfide fibers, polymoetheretherketone fibers At least one kind alone or more than two kinds of black may be used together.

Composition comprising any new novolak light ^"agent of the present invention, for example, the content of fibers in the glass fiber composite composition 10wt¾> to about 90wt% based on the total weight of the composition solids, for example, 30wt % To 70 wt%, and for example, 35 wt% to 65%. Further, in the cured product of the composition, for example, glass fiber composites, the fiber content is 10 wt% to 90 wt%, for example 30 wt% to 70 wt%, and for example 35 wt%, based on the total weight of the cured product. % To 65%. Thus, the resin content is lp _w t% to 90 wt%, for example. 30 wt% to 70 wt%. Also, for example, it may be 35wt% to 65wt%. It is preferable that the content of the fiber is in the above range in terms of heat resistance improvement and processability. On the other hand, in the composition containing a fiber, hardened | cured material, etc., the solid part except a fiber among the total solid content is normally called resin component, and in the composition containing a fiber, the quantity other than fiber is resin content (res in content).

Furthermore, any of the compositions of the present invention comprising the fibers may further comprise inorganic particles, if necessary. At this time, the inorganic particles are in the range of lwt¾ »to 70wt% based on the increase of the resin content in consideration of the improvement of physical properties and fairness. It can be formulated in amounts. At this time, the type of inorganic particles that can be used is not particularly limited, any inorganic particles known in the art can be used, for example, the type of the inorganic particles can be used.

According to another embodiment of the present invention, the composition according to any of the above and below embodiments of the present invention may further comprise an alkoxysilyl group reaction catalyst (hereinafter referred to as "banung catalyst") as needed. The composition containing the alkoxysilyl group reaction catalyst is called "reaction catalyst containing composition" for convenience. The reaction catalyst-containing composition also includes at least one new novolac curing agent selected from the group consisting of Formulas 1-1 to 1-4, and the reaction catalyst, and an epoxy resin constituting the composition, the curing agent of the present invention. It does not limit the kind and compounding ratio of the existing hardening | curing agent, a hardening accelerator (catalyst), an inorganic material (filler) (for example, inorganic particle and / or fiber), and other additives. The alkoxysilyl group reaction catalyst may be added for improved processability (eg, fast curing rate and / or low curing temperature).

When the alkoxysilyl group semicoagulant is included in the composition according to any embodiment of the present invention, the alkoxysilyl group semicoagulant is not limited thereto, but may include, for example, nitric acid, sulfuric acid, hydrochloric acid, acetic acid and phosphoric acid. At least one inorganic acid selected from the group, ammonia 4OH, NH ₄ 0H, amines and transition metal alkoxides, metal oxides, metal organic acid salts and halides (e.g. dibutyltin Dilaurate (di t butyl in di l aurate), tin salts of octylate, tin (II) ethyl 2- nuclear Sano benzoate) is used at least one kinds selected from the group consisting of ^"Tin _(n) compound), such as Can be. These may be used alone or in combination of two or more kinds. The blending amount of the alkoxysilyl group reaction catalyst is not particularly limited, but considering the reaction properties, the alkoxysilyl group semi-amplification catalyst is 0.01 phr to 10 to the epoxy resin of the present invention. can be used as phr. In order to improve the efficiency of the alkoxysilyl group reaction catalyst, water may be further included in the composition including the alkoxysilyl group reaction catalyst. In this case, the blending amount of water is not particularly limited, but may be 0.01 equivalent to 20 equivalents of water with respect to 1 equivalent of alkoxysilyl group in consideration of efficiency and reaction properties as a catalyst. In a composition comprising any of the novel novolak curing agents provided in the invention described above. Any curing accelerator (curing catalyst) may be further included as necessary to promote the curing reaction. Also, in the case of the novolak curing agent, to improve the reactivity with the epoxy resin. Hardening accelerators are usually used, and in view of the common technical knowledge of the art, it will be apparent to those skilled in the art that any of the above-mentioned and later described compositions may include a curing accelerator depending on the degree of curing reaction. Do. As the curing accelerator (curing catalyst), any catalyst known in the art to be generally used for curing the composition can be used, and thus Although, for example, a curing accelerator such as imidazole, tertiary amine, quaternary ammonium, organic acid salt, Lewis acid, phosphorus compound, etc. may be used. More specifically, for example, 2-methylimidazole (2MZ), 2-undecylimidazole, 2-ethyl 4'methylimidazole (2E4M), 2-phenylimidazole, 1 '(2 Imidazoles such as -cyanoethyl) -2-alkyl group imidazole and 2-heptadecylimidazole (2HDI); Tertiary amine compounds such as benzyl dimethyl amine (BDMA), trisdimethylaminomethylphenol (DMP-30), diazacycloundecene (DBU) and triethylenediamine; Quaternary ammonium salts such as tetrabutylammonium bromide; Organic acid salts of diazabicyclo undecene (DBU) and DBU; Phosphoric compounds such as triphenylphosphine and phosphate ester, Lewis acids such as BF ₃ -monoethyl amine (BFVMEA), and the like, and the like, and the like. These curing accelerators may be used as latent in their microcapsule coating and complex salt formation. These may be used independently and may use 2 or more types together according to hardening conditions. The compounding quantity of the said hardening accelerator is not specifically limited, It can mix | blend in the quantity generally used in this technical field, and can use. For example, the epoxy resin may be 0.1 to 10 phr (parts per hundred resin, parts by weight per 100 parts by weight of epoxy resin), for example, 0.2 to 5 phr. The curing accelerator is preferably used in the above content in terms of curing reaction promoting effect and curing reaction rate control. The curing accelerator in the compounding amount in the above range By using it, the curing progresses rapidly and the throughput can be expected to be improved. The composition is a release agent, surface treatment agent, flame retardant which is conventionally formulated for controlling the physical properties of the composition in a range that does not impair the physical properties of the composition. Plasticizers, antibacterial agents, leveling agents,. Other additives such as antifoams, colorants, stabilizers, coupling agents, viscosity modifiers, diluents, rubbers, thermoplastics, etc. may also be blended as needed. For example, in the case where a composition according to the present invention is formed into a thin film, a composition having insufficient flexibility may cause bridging to cause cracking. This is the case, for example, when any composition of the present invention contains a large amount of inorganic particles. Thus, rubber and / or thermoplastic resins may be added to compositions comprising any new novolac curing agent of the present invention to improve solubility in the composition. Thermoplastic resins and rubber-modified epoxy resins can be used that are generally known in the art. As the rubber, any rubber known in the art may be used as long as it is not dissolved in the solvent used in the composition and remains dispersed in the composition. Although not restrict | limited by this, As a kind of rubber, an acrylonitrile butadiene rubber, for example. Butadiene rubber, acrylic rubber, core-shell rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, acrylic rubber indenters and the like. These may be used alone or in combination of two or more. In the case of using the rubber particle form, the average particle diameter is preferably in the range of 005 to 1 / im in terms of physical properties, and 0.2 to The range of 0.6 is more preferable. Rubber particles, see the above _. Based on the weight of solids of the composition of the present invention, for example, in consideration of physical properties, it may be blended in an amount of 0.5 to 10% by weight. Thermoplastic resins include, but are not limited to, phenoxy resins, polyvinyl acetal resins. Polyimide resin, polyamideimide resin, polyether sulone resin, polysulfone resin and the like. These may be used alone or in combination of two or more. The thermoplastic resin may be blended in an amount of, for example, 0.5 to 60% by weight, preferably 3 to 50% by weight, based on the weight of the solid content of the composition of the present invention. As mentioned above. As used herein, the term "composition comprising a composition, a composition of the present invention or a new novolak curing agent" refers to an epoxy resin and the novolak curing agent of the present invention as well as other components constituting the composition as needed, for example, In addition to conventional curing agents, optional curing accelerators (catalysts), inorganic materials (fillers), for example inorganic particles and / or fibers, and solvents, may contain other additives formulated as needed in the art. It is understood that, therefore, in general, the solvent in the composition may optionally be used to appropriately adjust the solid content and / or viscosity of the composition in consideration of the processability of the composition and the like. On the other hand, the term "total weight of the solid content of the composition" used in the present invention refers to the total weight of the components excluding the solvent among the components constituting the composition described above. Any of the compositions of the present invention provided in any of the above embodiments of the present invention may be used for electronic materials. The electronic material is not limited to this, but, for example, not only a substrate build-up film for semiconductors, a prepreg, or a laminated plate on which a metal film is disposed on a substrate made of the composition of the present invention, but also a sealing material (packaging material), as well as printed wiring Electronic components such as substrates. It can also be applied to various applications such as adhesives, paints and composite materials. According to still another embodiment of the present invention, there is provided an electronic material comprising or consisting of any composition comprising the novolac curing agent of the present invention. Furthermore, there is also provided a semiconductor device comprising, consisting essentially of, or consisting of the electronic material. Specifically, the semiconductor device includes a semiconductor device and / or a semiconductor packaging material including (eg, mounting a semiconductor device) a printed wiring board comprising, or consisting essentially of, a composition comprising the novolac curing agent of the present invention. It may be a semiconductor device including a. Also provided are cured products, adhesives, paints, or composites comprising, consisting essentially of, or consisting of any of the compositions of the present invention provided in any of the embodiments of the present invention. According to another embodiment of the present invention, there is provided a cured product comprising, consisting essentially of, or consisting of the composition of the invention provided in any of the embodiments of the invention described above. The composition provided in any of the above-described embodiments of the present invention is used as a cured product when it is actually applied, for example, as an electronic material, and in the art, an epoxy resin and an inorganic component The cured product of the composition comprising the filler is generally referred to as a composite. The novel novolac curing agent provided in one embodiment of the present invention described above exhibits excellent heat resistance and excellent flame retardancy in the composite. Specifically, the composite has a low CTE, for example, 15 ppm / ° C. or less, for example 12 ppm / ^° C. or less. For example, a CTE of 10 ppm / ^° C or less, for example, 8 ppm / ^° C or less, for example, 6 ppm / ^° C or less, for example, 4 ppmni / ^° C or less. The smaller the CTE value is, the better the physical properties are, and the CTE value is not particularly limited. For example, a novel novolac curing agent according to the present invention as a curing agent, oil ^ fiber as an inorganic material, for example, E-glass and / or T-glass glass fiber. The resin content of 30wt% to 60wt% (may have include an inorganic particles-resin ^content, that may not be included) in the composite are, for example, 10ppm / ^° C or less, for example, 8ppm / ^° C or less, e. For example, 6 ppm / ^° C. or less, for example, 4 ppm / ° C. or less CTE. Further, for example, any novel novolac curing agent according to the present invention as a curing agent, a composite containing 60 to 80wt%, for example, 70 to 80wt% of inorganic particles, for example, silica particles as an inorganic material, 20ppmrc or less, For example, 15 ppm / ^° C or less, for example, 10 ppm / ^° C or less, for example, 8 ppm / ^° C or less, for example, 6 ppm / ^° C Hereinafter, for example, CTE of 4 ppm / ^° C or less is shown. In addition, the composite according to the present invention (cured product containing an inorganic material) may have a T _g higher than locrc, for example, 130 ^° C or more, for example, 250 ^° C or more, or Tg-less. . The Tg value is excellent in Kk-Tock physical properties and does not particularly limit the upper limit of Tg. In the present specification, the value indicated by the range means that each includes not only the lower limit value and the upper limit value of the range, but also any lower range between the ranges and all the numbers belonging to the range. For example, C1 to C10 are CI, C2, C3, C4. It is understood to include all of C5, C6, C7, C8, C9, C10. In addition, the lower limit value or the upper limit value of the numerical range is not specified, and the smaller or larger the value is, the more preferable. It is understood to include any value. For example, a CTE below 4 ppm / ^° C is understood to include all values between 4, 3.5, 3, 2.7, 2, 1.4, 1, 0.5 ppm / ^° C, and the like. Hereinafter, the present invention will be described in detail with reference to Examples. The following examples illustrate the invention but do not limit the invention. Synthesis Example 1 Synthesis of Silylated Phenol Novolac Curing Agent 15 g of a phenol novolac curing agent (Formula 1, Meiwa Plastic Ind., Trade name HF-1M), 8.67 g of triethoxysilyl propyl isocyanate, and 150 ml of tetrahydrofuran (THF) were mixed, and then filled with argon. Stir at room temperature for 15 hours. After reaction, the solvent was removed using an evaporator, and the concentration ratio of the hydroxyl group and the silyl functional group of the novolak curing agent. In other words, a silylated novolac curing agent having a ratio of [OH]: [Si] = 3.9: 1 was obtained. The NMR data of the obtained final product is as follows.

[Formula 1]

NMR (400MHz, DMS0): δ = 9.43-8.93 (m, 3.89H), 7.71 (s, 0.97H), 7.26-6.51, (m, 20.71H), 3.94-3.55 (111, 16.33H), 3.15 -2.89 (m, 2.57H), 1.62-1.44 (m, 2.61H), 1.19-1.04 (m, 11.98H), 0.66-0.43 (m, 2.46H) Synthesis Example 2 Synthesis of silylated phenol novolac curing agent Synthesis was carried out in the same manner as in Synthesis Example 1, except that 11.44 g of triethoxysilyl propyl isocyanate was used, and the concentration ratio of the hydroxyl group and the silyl functional group of the novolak curing agent, that is, [OH]: [Si] = 2.6: 1 Having silylated phenol nobulac A curing agent was obtained.

¾ NMR (400 MHz, DMSO): δ = 9.43— 8.93 (ni, 3.11 H), 7.71 (s, 1.47 H), 7.26-6.51 (m, 20.21 H), 3.94-3.55 (m, 18.55 H), 3.15- 2.89 (m, 3 ₄ 57H), 1.62-1.44 (m, 3.48H), 1.19-1.04 (m, 15.09H), 0.66-0.43 (m, 3.63H) Synthesis Example 3: Synthesized silylated phenol nobulac curing agent

(1) First step: 10 g of a phenol novolac curing agent (Formula 1, Meiwa Plastic IncL, trade name HF-1M), 3.74 g of NaOH, and 250 ml of DMSO were added to the flask, and the phase was stirred for 30 minutes. Thereafter, the temperature was lowered to 0 ° C. and 2.26 g of allyl bromide was added thereto, followed by stirring at room temperature for 2 hours. After the reaction, the mixture was worked up using 400 ml of ethyl acetate and saturated NaCl solution, the organic layer was separated, MgS0 ₄ was added to the organic layer to remove the remaining ¾0, filtered through a celite filter, and the solvent was removed using an evaporator. Thus, an allylated novolac curing agent having a functional group concentration, that is, a ratio of [0H]: [allyl group] = 4: 1 was obtained. The R data of the obtained final product is as follows. [Formula 1]

¾ NMR (400 MHz, DMSO): δ = 7.14-6.70 (m, 21.68H), 6.04-6.00 (m, 1.35H), 5.41-5.20 (ni, 2.98H), 4.49-4.47 (m, 3.01H), 4.17-3.80 (m, 11.8H)

(2) Step 2: After mixing 10 g of the allylated novolac curing agent obtained in Step 1, 2.85 _{g of} Triethisilane, 79 _m g of platinum oxide, and 100 ml of toluene into a flask, Stir at 85 ° C. for 24 hours. After the reaction, the obtained crude product was filtered through Celite and the solvent was removed using an evaporator to obtain a silylated phenol having a ratio of the hydroxyl group and silyl functional group of the no-opaque curing agent, that is, [OH]: [Si] = 1: 1. A novolac curing agent was obtained. The NMR data of the obtained final product is as follows.匪 R (400 MHz.DMSO): δ = 9.31 (br.s, 4.92H), 7.14-6.70 (m, 21.68H), 4.17-3.80 (m, 25.23H), 1.82-1.70 (m, 2.78H), 1.24-1.20 (m, 12.99 H), 0.80-0.61 (m, 2.60 H) Synthesis Example 4 Synthesis of Silylated Noblock Curing Agent (Phenol Araki Resin) 15 g of a novolac curing agent (Mitsui Chemicals Inc., trade name XLC-4L) having Structural Formula 2 in a flask, 7.31 g of triethoxysilyl propyl isocyanate, and tetra 150 ml of hydrofuran (THF) was added and mixed, followed by stirring in phase silver for 15 hours in an argon-filled state. After the reaction, the solvent was removed using an evaporator to obtain a silylated novolac curing agent having a concentration ratio of the hydroxyl group of the novolak curing agent and the silyl product vessel, that is, the ratio [OH]: [Si] = 2: 1. The NMR data of the obtained final product is as follows.

[Formula 2]

NMR (400 MHz, DMS0): 5 = 9.31 (br.s, 3.66H), 7.75 (br.s, 1.98H), 7.08-6.68 (m 19.91H), 4.20-3.79 (m, 12.84H), 3.32 -3.12 (m, 4.73H), 1.72-1.54 (m, 4.27), 1.24-1.20 (m, 18.72H), 0.80-0.61 (m, 4.17H).

Synthesis Example 5 Synthesis of Silylated Noble Curing Agent (Biphenyl Aralkyl Type Phenolic Resin) 15 g of biphenyl novolac curing agent (Formula 3, Meiwa Plastic Ind., Trade name MEH-7851SS), 4.57 g of trioxysilyl propyl isocyanate, and 150 nil of tetrahydrofuran (THF) were added to the flask, followed by mixing. Stirred at room temperature for 15 hours. After the reaction. The solvent was removed using an evaporator to obtain a silylated novolak curing agent having a concentration ratio of the hydroxyl group and the silyl functional group of the novolak curing agent, that is, the ratio [OH]: [Si] = 3: 1. The NMR data of the obtained final product is as follows.

[Formula 3]

NMR (400MHz, DMS0): 9.41 (s, 0.78H), 9.26 (s, 0.29H), 9.21 (s, 0.59H), 7.88-6.61 (m, 20.40H), 4.05-3.70 (m, 8.27H ), 3.15-2.85 (m, 1.15H), 1.69-1.45 (m, 1.12H), 1.28-1.05 (m, 5.86H), 0.67-0.42 (m, 1.16H), Synthesis Example 6: Silyzed dish Into the clopentadiene novolac curing agent synthetic flask, 15 g of dicyclopentadiene novolac curing agent (Formula 4, Nippon petrochemicals Co., trade name DCPDP), 3.53 g of triethoxysilyl propyl isocyanate and 150 ml of tetrahydrofuran (THF) After adding, with argon charged Stir at room temperature for 15 hours. After the reaction, the solvent was removed using an evaporator to obtain a silylated novolac curing agent having a concentration ratio of the hydroxyl group and the silyl functional group of the novolak curing agent, that is, [OH]: [Si] = 4: 1 ratio. The NMR data of the obtained final product is as follows. Structural Formula 4]

MR NMR (400 MHz, .DMS0): δ = 9.30 (br.s, 3.11H), 7.80 (br.s, 0.76H), 7.39-6.59 (m ₇ 23.00H), 3.79-3.51 (m, 7.88H) , 3.10-2.61 (m, 8.18H), 2.25-1.00 (m. 50.26H), 0.65-0.51 (ni, 1.61H) Synthesis Example 7: Synthesized silylated novolac hardener synthesis (polyfunctional phenolic resin) 15 g of a polyfunctional novolac curing agent (Formula 5, Meiwa Plastic Ind., MEH-7500-3S), 7.22 g of triethoxysilyl propyl isocyanate, and 150 ml of tetrahydrofuran (THF) were mixed, and then filled with argon. ^, and the mixture was stirred at 15 for phase time status. After the reaction, the solvent was removed using an evaporator to obtain a silylated novolac curing agent having a concentration ratio of the hydroxyl group and the silyl functional group of the novolak curing agent, that is, the ratio [OH]: [Si] = 4: 1. NMR of the final product obtained The data is as follows.

[Structure 5]

¾ NMR (400MHz, DMS0): 6 = 9.19 (br.s, 6.29H), 7.05-6.51 (m, 26.00H), 5.91 (s, 0.57H), 5.58 (m, 0.74H), 3.87-3.45 ( m, 12.75H), 3.15-2.91 (m, 3.72H), 1.54- 1.48 (m, 3.90H), 1.20-1.16 (m, 18.45H), 0.67-0.50 (m, 3.33H) Synthesis Example 8: Silyl localized-cresol novolak curing agent cresol novolak curing agent in synthesis (Structure 6, DIC Corporation. Co., trade name: KA-1163) 15g, ^then, into the silyl-ethoxy propyl isocyanate and 6.29g tetrahydrofuran (THF) 150ml shake combined the tree Stir at phase silver for 15 hours with argon charged. After the reaction, the solvent was removed using an evaporator to obtain a silylated novolac curing agent having a concentration ratio of the hydroxyl group and the silyl functional group of the novolak curing agent, that is, the ratio [OH]: [Si] = 4: 1. The NMR data of the obtained final product is as follows.

Ν.Ν 服 (400MHz, DMSO): 5 = 9.32 (br.s, 2.99H), 7.77 (br.s, 0.77H), 7.02-6.89 (m, 10H), .4.24-3.36 (m, 12.25H ), 3.18-3.01 (m, 1.89H), 2.24-2.10 (m, 12.88H), 1.73—1.40 (m, 1.88H), 1.20-1.14 (m, 9.99H), 0.64-0.50 (m, 1.60H) Synthesis Example 9: 15 g of bisphenol A novolac curing agent (Formula 7, DIC Corporation., Trade name VH-4150) in a silylated bisphenol A novolac curing agent synthesis flask, 6.29 g of triethoxysilyl propyl isocyanate and tetra After hydrofuran (THF) 150nil was added and mixed, the mixture was stirred at room temperature for 15 hours in an argon-laminated state. After the reaction, the solvent was removed using an evaporator to obtain a silylated novolac curing agent having a concentration ratio between the hydride of the novolak curing agent and the silyl functional group, that is, the ratio [OH]: [Si] = 4: 1. The NMR data of the obtained final product is as follows. [Structure 7]

¾ NMR (400 MHz, DMSO): 5 = 9.31 (br.s, 7.65H), 7.76 (br.s, 1.76H), 7.20-7.05 (m. 16.00H), 6.89-6.75 (m, 17.58H), 4.22-3.79 (m, 37.28H), 3.36-3.28 (m, 4.23H), 1.62-1.20 (m, 62.11H), 0.67-0.51 (m, 3.95H) Synthesis Example 10: Silylated naphthalene novolac hardener 15 g of naphthalene novolac curing agent (Scheme 8, Nippon Kayaku C, KAYAHARD CBN), 5.38 g of triethoxysilyl propyl isocyanate, and 150 ml of tetrahydrofuran (THF) were mixed, and then mixed with argon. Stir at phase silver for 15 h. After the reaction, the solvent was removed using an evaporator to obtain a silylated novolac curing agent having a concentration ratio of the hydroxyl group and the silyl functional group of the novolak curing agent, that is, [OH]: [Si] = 4: 1 ratio. The XR data of the obtained final product is as follows. [Structure 8]

n

NMR (400 MHz, DMSO): δ = 9.30 (br.s, 3.51H), 7.75 (br.s 0.72H), 8.03- 7.51 (m, 11.99H), 7.39-6.85 (m, 15.43H), 4.40 -3.60 (m, 23.77H), 3.35-3.25 (m. 2.30H), 1.69-1.38 (m, 2.21H), 1.21-1.05 (m, 11.88H), 0.68-0.45 (m, 1.92H) Hardening Preparation and Heat Resistance Evaluation

1. Epoxy Composite Manufacturing

(1) Preparation of epoxy glass fiber composite (cured product) With the composition shown in Table 1, epoxy compound, and silica slurry (solid content of 70wt%, methyl ethyl ketone solvent, average silica size 1 / ΛΙΙ) of Ν, Ν-dimethyl Dissolve in acetamide to 40% solids. After mixing this mixed liquid at the speed of 1500 rpm for 1 hour, the hardening | curing agent was added and it mixed for further 50 minutes. After that, here. Finally, the curing catalyst was added and further mixed for 10 minutes to obtain a binder solution containing a silyl curing agent. An epoxy glass fiber composite containing a silylated curing agent was prepared by immersing glass fiber (N-Ttobo, T-glass) in this binder solution. The composite was then placed in a vacuum oven heated to 100 ^° C to remove the solvent and then preheated to 12 CTC. The glass fiber composite was obtained by curing at a hot press for 2 hours at 120 ^° C., 2 hours at 180 ^° C. and 2 hours at a temperature of 200 ^° C.-230 ° C.

(2) Preparation of Epoxy Filler Composite (Hardened) According to the composition shown in Table 2 below, epoxy compound, silica slurry (dispersion solution: methyl ethyl ketone solvent, silica average size 1) and polyvinyl acetal Ν, Ν ᅳ dimethylacet Dissolve the amide to 40% solids. The mixture was mixed for 1 hour and 30 minutes at a speed of 1500 rpm, followed by addition of a hardening agent and further mixing for 30 minutes. 2-2 hours the common compound at 100 ^° to put the vacuum Bon Festival heated to C, remove the solvent in a hot-press pre-heated to 120 ^{^°} C 120 ^° C, in a 180 X 2 hours and 200 ^° C ~ 230 ° C Curing to give an epoxy filler (inorganic particle) composite (5 × X 5 × X 3 ′).

2. Heat resistance property evaluation

In order to evaluate the heat resistance characteristics of the composite prepared by the above method, the dimensional change according to the degree of silver is evaluated using a thermo-mechanical analyzer (Therm mechanical analysizer) is shown in Table 1 and Table 2. 1 shows the results obtained in Example 1 and Comparative Example 1 (Table 1). At this time, the specimen of the glass fiber composite film is 4X 16X0. A size of K讓^3), the specimen of the composite filler was prepared by the size of 5X5X3 (匪^3).

As shown in Table 1, Table 2 and Figure 1 the cured product obtained by the present invention It was confirmed that the glass transition temperature was not shown (Tg-ess). In the following Table 1 and 2 in the case of the composite with a glass transition temperature, the glass transition temperature before (Τ <') and after the glass transition temperature (T> Tg), the CTE value is different, it is represented as _αι and α ₂ , respectively. Therefore, on (T <Tg) means the CTE value between the silver tools before the glass transition temperature. On the other hand, since the CTE of the composite sample typically uses _αι values, (T <T _g ) values are shown in Tables 1 and 2 below.

Table 1 Glass Fiber Composites

Table 2 Filler Composite

Note: The compounds used in Tables 1 and 2 above are as follows.

(1) DGEBA: Diglycidyl ether of bisphenol A, Aklrich, EE = 190

(2) EXA4700: Binaphthalene epoxy (EEW = 162, DIC Corporation)

(3) YX4000H: Biphenyl epoxy

(4) polydis: rubber modified epoxy (Strrukt)

(5) HF-1M: phenol novolac curing agent (Meiwa Plastic Industries, HEW = 107)

(6) TPP: triphenylphosphine (Aldrich)

(7) 2E4MZ: 2 ᅳ ethyl-4-methyl imidazole (Aldrich) As shown in Table 1, Examples 1 to 12 containing the novolak curing agent having an epoxy resin of the present invention and an alkoxysilyl group The composite exhibits not only low CTE but also glass transition temperature compared to the composites of Comparative Examples 1 and 2 including an epoxy resin having no alkoxysilyl group and a conventional novolak curing agent (Tg ᅳ less, TgL), It was found that the heat resistance was improved 향상

Claims

【Patent Claims】【Claim 1】 A novolak curing agent having one alkoxysilyl group and having the following formulas 1-1 to 1-4. [Formula 1-1] (In the above formula I 1, Z is one of the groups consisting of the following formulas 1A to 1F. 1A 1B 1C [Formula I 2] It is an alkyl group. ) (In the above formulas 1-1 to 1-4, at least one A is the formula A2 or A3, and when at least one is A2, the remaining A is the formula B2 or hydrogen, and is written as H c When one of the 2 is A3, the remaining A is hydrogen, and n is an integer of 1 or more. ) [Formula A2] -(CH2)m-SiRiR2R3 [Formula A3] -C0NH(CH2)m-SiRiR2R3 (Formula A2 And in A3, at least one of to R3 is a straight-chain or branched alkoxy group having 1 to 5 carbon atoms, the remainder is a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and m is an integer of 3 to 10. ) [Chemical formula B2] -(CH2) CH=CH2 (wherein, 1 is an integer from 1 to 8.) [Claim 2] In the presence of a base and an optional solvent, a starting material of one of the following formulas IA-1 to IA-4 and the following formula A first step of reacting an alkenyl compound of Π to form an intermediate product of the following formulas IB-1 to IB-4; And one of the formulas 1-1 to 1-4 having the structure of formula A2 by reacting an intermediate product of the formulas IB-1 to IBᅳ 4 with an alkoxysilane of the formula ΙΠΑ in the presence of a platinum catalyst and an optional solvent. A method for producing a novolak curing agent having any one alkoxysilyl group selected from the group consisting of Formulas 1-1 to 1-4, including a second step of forming a compound of. [Formula IA-1] (In the above formula IA-1, ' 1 or 2, xl is and R is a C1-C10 linear or branched alkyl group. ) (In the above formulas IA-1 to IA-4, n is an integer of 1 or more.)

[Formula IB-1]

(In the above formula, Y1 is one of the groups consisting of the following formulas 3A to 3F.

[Formula IB-2]

[Formula IB-3]

[Formula IB-4]

(In the above formula IB-4, p is 1 or 2 and

x2

and

R is a straight or branched C1-C10 alkyl group. )

(In the above formulas IB-1 to IB-4, at least one D is the formula B2 below and the remainder may be hydrogen, and n is an integer of 1 or more.) [Formula B2]

-(CH ₂ ) CH=CH ₂

(In the formula, 1 is an integer from 1 to 8.)

[Formula Π]

X-(CH ₂ ),-CH=CH ₂

₍ _Wherein , 1 is _an integer _from ₁ _to ₈ , _and am.)

[Chemical formula ΠΙΑ]

HSiR _a R _bc

(In the above formula, at least one of R _a to R _c is a straight-chain or branched C1-C5 alkoxy group, and the remainder is a straight-chain or branched C1-C10 alkyl group.)

[Formula 1-1]

(In the above formula, Z is one of the groups consisting of the following formulas 1A to 1F.

92 [Formula 1-3]

[Formula 1-4]

(In Formula 1-4, p is 1 or 2 and

and

R is a linear or branched alkyl group of CI—CIO. )

(In the above formulas 1-1 to 1-4, at least one A is the formula A2 and the rest are the formula B2 or hydrogen, and n is an integer of 1 or more.) [Formula A2]

-(CH ₂ ) _m -SiRiR ₂ R ₃

(In the above formula A2, at least one of ¾ to ¾ is a straight-chain or branched alkoxy group having 1 to 5 carbon atoms, the remainder is a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and m is an integer of 3 to 10.)

[Formula B2]

-(CH ₂ ) ,-CH=CH ₂

(In the formula, 1 is an integer from 1 to 8.) [Claim 3]

The method of claim 2, wherein in the first step, the alkylene group of the alkenyl compound of the formula Π is 0.1 to 10 equivalents relative to 1 equivalent of the hydroxy group of the starting material of one of the formulas IA-1 to IA-4. A method for producing a novolak curing agent having an alkoxysilyl group, which is carried out by reacting to achieve this.

【Claim ⁴ 】

The method of claim 2, wherein the first step is performed by reacting at -20 ^° C to 100 ^° C for 1 hour to 120 hours.

[Claim 5]

The method of claim 2, wherein the second step is performed by reacting an alkoxysilyl group in an amount of 0.1 to 5 equivalents of alkoxysilane relative to 1 equivalent of an alkenyl group of an intermediate product of formulas IB-1 to IB-4. Method for producing a novolac hardener having.

【Claim 6】

The method of claim 12, wherein the second step is carried out by reacting at 20°C to 12CTC for 1 hour to 72 hours.

【Claim 7】

In the presence of any base and any solvent, a starting material of one of the following formulas IA-1 to IA-4 and an alkoxysilane of the following formula ΠΙΒ are reacted to produce one of the formulas 1—1 to 1ᅳ4 having the structure of formula A3. Method for producing a novolak curing agent having any one alkoxysilyl group selected from the group consisting of Formulas 1-1 to 1ᅳ4, including an alkoxysilylation step to form a compound.

[Formula IAᅳ 1]

(In the above formula (IA-1),

96 [Formula IA-4]

(In Formula IA-4, p is 1 or 2,

XL

and

，R is a C1-C10 straight or branched alkyl group. )

(In the above formulas IA-1 to IA-4, n is an integer of 1 or more.)

[Chemical formula ΙΠΒ]

0CN-(CH ₂ ) _m -SiR ₁ R ₂ R ₃

(In the above chemical formula ΙΠΒ, at least one of the groups 1 to ¾ is a straight-chain or branched alkoxy group having 1 to 5 carbon atoms, the remainder is a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and !^ is an integer of 3 to 10.) [Formula 1-1]

1A IB 1C

[Formula 1ᅳ2]

[Formula 1-3]

[Formula Iᅳ 4]

(In Formula 1-4, p is 1 or 2 and

Ο

C.H.,

and

Where R is a C1-C10 straight or branched alkyl group.)

(In the above formulas 1-1 to Iᅳ 4, at least one A is the formula A3 below, the rest are hydrogen, and n is an integer of 1 or more.) [Formula A3]

(In the above formula A3, at least one of R _{3 to R 3} is a straight-chain or branched alkoxy group having 1 to 5 carbon atoms, the remainder is a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and m is an integer of 3 to 10.)

【Claim 8】

The method of claim 7, wherein the alkoxysilylation step is performed by reacting the alkoxysilane in an amount of 0.1 to 5 equivalents based on 1 equivalent of the hydroxyl group of one of the starting materials of formulas I A-1 to IA-4. A method for producing a novolak curing agent having an alkoxysilyl group.

【Claim 9】

The method of claim 7, wherein the alkoxysilylation step is performed by reacting at -20 ^° C to 120 ^° C for 1 hour to 72 hours.

[Claim 10]

A composition comprising an epoxy resin and a novolak curing agent having at least one alkoxysilyl group selected from the group consisting of the following formulas (Ieu) 1 to 1-4. [Formula 1-1]

1A 1B 1C

[Formula 1-4]

(In Formula 1-4, p is 1 or 2 and

and

R is a straight or branched alkyl group of Ci-αο. )

(In Formulas 1-1 to 1—4,

At least one A is of the following formula A2 or A3, and when at least one is A2 The remaining A is the formula B2 or hydrogen, and when at least one is A3, the remaining A is hydrogen, and n is an integer of 1 or more. )

[Formula A2]

-(CH ₂ ) _m -SiR!R ₂ R ₃

[Formula A3]

-C0NH(CH ₂ ) _m -SiRiR ₂ R ₃

(In the above formulas A2 and A3, at least one of ¾ to ¾ is a straight-chain or branched alkoxy group having 1 to 5 carbon atoms, and the remainder is a straight-chain or branched alkyl group having 1 to 10 carbon atoms. m is an integer of 3 to 10. )

[Formula B2]

-(CH ₂ ) ,-CH=CH ₂

(In the formula, 1 is an integer from 1 to 8.)

【Claim 11】

The method of claim 10, wherein the epoxy resin is at least one selected from the group consisting of glycidyl ether-based epoxy resin, glycidyl-based epoxy resin, glycidylamine-based epoxy resin, and glycidyl ester-based epoxy resin. Composition.

【Claim 12】 ^.

The method of claim 11, wherein the epoxy resin has a core structure of bisphenol, biphenyl, naphthalene, benzene, thiodiphenol, fluorene, anthracene, isocyanurate, triphenylmethane, 1, 1, 2, 2. -Tetraphenylethane, tetraphenylmethane, 4,4'-diaminodiphenylmethane, aminophenol, cycloaliphatic, aliphatic. or a composition having a novolak unit,

【Claim 13】

The composition of claim 11, wherein the epoxy resin includes an epoxy resin with or without an alkoxysilyl group.

【Claim 14】

The composition according to claim 10, further comprising at least one filler selected from the group consisting of inorganic particles and fibers.

【Claim 15】.

The method of claim 14, wherein the inorganic particles are silica, zirconia, titania, or alumina. A composition that is at least one selected from the group consisting of silicon nitride, aluminum nitride, and silsesquioxane.

【Claim 16】 _{. .}

The composition according to claim 14, wherein the inorganic particles are contained in an amount of 5 wt% to 95 wt% based on the total weight of solid content of the composition.

【Claim 17】

In clause 16. A composition in which the inorganic particles are contained in an amount of 30 wt% to 95% based on the total weight of solid content of the composition.

[Claim 18]

The composition according to claim 16, wherein the inorganic particles are contained in an amount of 5 wt% to 60% based on the total weight of solid content of the composition.

[Claim 19]

The method of claim 14, wherein the fiber is glass fiber selected from the group consisting of E glass fiber, T glass fiber, S glass fiber, NE glass fiber, H glass fiber, and quartz; and liquid crystal polyester fibers, polyethylene terephthalate fibers, wholly aromatic fibers, polybenzoxazole fibers, nylon fibers, polyethylene naphthalate fibers, and polypropylene fibers. Polyether sulfone fiber. A composition that is at least one kind selected from the group consisting of organic fibers selected from the group consisting of polyvinylidene fluoride fibers, polyethylene sulfide fibers, and polyetheretherketone fibers.

[Claim 20]

The composition of claim 19, wherein the fiber is E glass fiber.

【Claim 21】.

The composition of claim 19, wherein the fiber is T glass fiber.

[Claim 22]

The composition of claim 14, wherein the fiber is contained in an amount of 10 wt% to 90% based on the total weight of solid content of the composition.

【Claim 23】

The composition according to claim 14, wherein when the filler includes fiber, the composition further includes inorganic particles.

[Claim 24] The composition of _claim 10, further comprising an alkoxysilyl group reaction catalyst.

【Claim 25】

The method of claim 24, wherein the alkoxysilyl group reaction catalyst is selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, ammonia, KOH, NH ₄ OH, amine, transition metal alkoxide, and tin (t in) compound. At least one kind of composition.

【Claim 26】

The method of claim 24, wherein the reaction catalyst is used in an amount of 0.01 phr to ^. A composition comprising 10 phr.

【Claim 27】

25. The composition of claim 24, further comprising water. 【Claim 28】

An electronic material comprising the composition of any one of claims 10 to 27. IClaim 】

A substrate comprising the composition of any one of claims 10 to 27. , 【Claim 30】

A film comprising the composition of any one of claims 10 to 27. 【Claim 31】

A laminate comprising a metal layer on a base layer made of the composition of any one of claims 10 to 27. 【Claim 32】

Printed wiring board including the charging board of clause 31. 【Claim 33】

A semiconductor device comprising the printed wiring board of claim 32. [Claim 34]

A semiconductor material comprising the composition of any one of claims 10 to 27. [Claim 35]

A semiconductor device comprising the semiconductor packaging material of claim 34. 【Claim 36】

An adhesive comprising the composition of any one of claims 10 to 27. 【Claim 37】

Paint containing the composition of any one of claims 10 to 27 - [Claim 38]

A composite material comprising the composition of any one of claims 10 to 27. 【Claim 39】

‘Prepreg’ comprising the composition of any one of claims 10 to 27. 【Claim 40】

A red plate in which a metal layer is disposed on the prepreg of item 39. 【Claim 41】

A cured product of the composition of any one of claims 10 to 27. 【Claim 42】

The cured product of claim 41, wherein the composition has a thermal expansion coefficient of 60ppm/ ^° C or less. ΓClaim 43]

The cured product of claim 41, wherein the cured composition has a glass transition degree higher than 100 ^° C or does not exhibit a glass transition temperature.