KR101003046B1 - Flame retardant and phosphorous-modified hardener and use thereof - Google Patents

Abstract

PURPOSE: A resin composition includes a phosphorous-modified flame retardant hardener with a UV shielding property, excellent flame resistance, adhesive property, and mechanical and chemical properties. CONSTITUTION: A resin composition comprises a phosphorous-modified flame retardant hardener with a UV shielding property selected from compounds represented by chemical formulas 7 - 8. The flame retardant hardener is included in the amount of 10-50 weight% based on 100 weight% resin composition. A UV shielding efficiency of the resin composition is 95% or more in UV region of 100 ~ 400 nm.

Description

인 Flame retardant and phosphorous-modified hardener and use

The present invention relates to a phosphorus modified flame retardant curing agent having excellent UV shielding performance and its use, and more particularly, to a phosphorus modified flame retardant curing agent having excellent UV shielding performance and at the same time having a flame retardancy and heat resistance characteristics and a use thereof will be.

Currently, plastics are widely used in various industrial fields such as electrical equipment, transportation equipment, and building materials, but most of them need to be flame-retardant in consideration of safety in case of fire due to the characteristics of being easily burned with organic materials such as carbon, oxygen, and hydrogen. This is constantly increasing. Generally, fuel, oxygen and energy are necessary for a fire to occur. If any of these conditions are not met, a fire cannot occur. In other words, one method of flame retardant plastics can be implemented by eliminating one or more of the three factors that cause fire. Flame-retardant curing agents are chemically or physically added to a polymer material having a property of easy combustion, such as halogen-based, phosphorus-based, nitrogen-based, or metal products, to slow the ignition and prevent the expansion of combustion. Say.

Flame retardant curing agents are divided into various types according to the end use, and can be divided into reactive and additive types. Reactive flame-retardant curing agent is a type of chemical reaction with functional groups in the molecule and is a flame-retardant curing agent that lasts flame-retardant effect without being greatly influenced by external conditions.Additional flame-retardant curing agent is physically mixed, added, and dispersed in plastic to achieve flame retardant effect Obtained mainly used in thermoplastics.

There are various types of additive or reactive flame retardants known to date, and the additive flame retardants include tricresyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tributyl phosphate, tris (bromo chloropropyl) phosphate and tris ( Dichloropropyl) phosphate and the like, and examples of the reactive flame retardant include bromo phenol, bromo phenyl allyl ether, vinyl chloroacetate, antimony glycol, tetrabromobisphenol A and the like.

Reactive flame retardants are chemically reacted with the substrate and are therefore mixed forever in the polymer structure, but since additive flame retardant systems do not cause chemical reactions with flame retardant and polymeric substrates, the added flame retardant is simply a substrate. It is often dispersed or dissolved in and lost from the substrate.

On the other hand, in electronic applications such as high density multilayer printed circuit boards, quality control of laminates has been carried out through automatic optical inspection (AOI). AOI is typically performed by measuring ultraviolet (UV) absorbance at a wavelength in the range of 450 nm to about 650 nm, for which it provides UV shielding properties using raw materials with UV blocking effect. Generally, resin composition for manufacturing printed circuit board is bisphenol-A Type Epoxy, Phosphorus Modified Epoxy, Novolac Epoxy, Tetra-phenyl ethane Epoxy, etc. as epoxy to phenolic compounds, where Tetra-phenyl ethane Epoxy is used to give UV shielding performance. And a substance such as fluorescent brightener is added to give better UV shielding performance. The curing agent of the resin composition for manufacturing a printed circuit board is a type that can be thermally cured. Dicy, DDS, DDM, phenol novolak, cresol novolak, and bisphenol anovolak curing agents are generally used. Resin for manufacturing printed circuit board should have good flame retardant property, good adhesion to substrate such as copper or aluminum or polyimide film, high glass transition temperature, high dimensional stability, low moisture absorption and UV shielding performance, Since the raw materials do not contain materials having flame retardant properties (halogen-based, phosphorus, nitrogen, etc.), the fire retardant properties and physical properties of the resin for printed circuit board manufacturing are poor.

In the case where a phosphorus compound (non-halogen series) is added in order to impart flame retardancy to a resin containing a phenolic compound, the flame retardancy may be improved. However, the reactive flame retardant is a type that reacts chemically with functional groups in the molecule, and has a flame retardant effect without being greatly influenced by external conditions, whereas the added flame retardant is simply dispersed or dissolved in the substrate and often lost from the substrate. In addition, the flame retardant properties are inferior to the reactive type. In addition, the addition flame retardant does not participate in the reaction during the curing reaction with epoxy, the glass transition temperature is reduced, the thermal stability is poor, in particular, the physical and chemical properties such as remarkably poor adhesion properties with the material occurs a disadvantage that occurs Have.

The present invention has been made to solve the above-mentioned problems, the first problem to be solved of the present invention is a modified flame retardant phosphorus having a UV shielding performance, excellent flame retardant properties, adhesion, mechanical and chemical properties without containing a halogen compound It is to provide a method for producing a curing agent.

The second problem to be solved of the present invention is to provide a resin composition comprising a novel phosphorus modified flame retardant curing agent that simultaneously satisfies UV shielding performance, excellent flame retardant properties, adhesion, mechanical and chemical properties.

A third object of the present invention is to provide a resin composition for a printed circuit board comprising the resin composition of the present invention and a printed circuit board including the same.

In order to achieve the above-mentioned first object, the present invention provides a phenol compound (1); And UV shielding performance comprising the step of preparing a flame retardant by performing a novolak reaction with an aldehyde-based compound of any one or more phosphorus-modified phenolic compound (2) of the compound represented by the formula 1 to 2 under an acid catalyst It provides an excellent method for producing a phosphorus modified flame retardant curing agent.

[Formula 1]

[Formula 2]

,

또는

이고,
R₂ 및 R₃는 각각 독립적으로 H, 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 또는 시아노이거나; 또는
치환 또는 비치환된 C₁ ~ C₁₀의 알킬, 치환 또는 비치환된 C₁ ~ C₁₀의 알케닐, 치환 또는 비치환 C₁ ~ C₁₀의 알키닐, 또는 치환 또는 비치환된 C₁ ~ C₁₀의 방향족 화합물, 치환 또는 비치환된 C₁ ~ C₁₀의 아실, 치환 또는 비치환된 C₁ ~ C₁₀의 헤테로 알킬이고, 상기 치환은 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 및 시아노 중 어느 하나 이상에 의한 것이고;
X는 각각 독립적으로 H 이거나; 또는
치환 또는 비치환된 C₁ ~ C₁₀의 알킬기로서, 상기 치환은 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 및 시아노 중 어느 하나 이상에 의한 것이고;
Y는 각각 독립적으로 S 또는 SO₂ 이거나; 또는
치환 또는 비치환된 C₁ ~ C₁₀의 알킬기로서, 상기 치환은 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 및 시아노 중 어느 하나 이상에 의한 것이고;R ₁ in Formulas 1 to 2 are each independently

,

or

ego,
R ₂ and R ₃ are each independently H, alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, or cyano; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl, substituted or unsubstituted C ₁ to C ₁₀ alkenyl, substituted or unsubstituted C ₁ to C ₁₀ alkynyl, or substituted or unsubstituted C ₁ to C ₁₀ aromatic compounds, substituted or unsubstituted C ₁ to C ₁₀ acyl, substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl, the substitution being alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy , Thiol, and cyano;
Each X is independently H; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl group, wherein the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano;
Each Y is independently S or SO ₂ ; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl group, wherein the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano;

delete

delete

n is independently an integer of 1-2.

According to a preferred embodiment of the present invention, the phenolic compound (1) may be any one or more of the compounds represented by the following formula (3).

(3)

[Formula 4]

X in Formulas 3 to 4 are each independently H; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl group, wherein the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano;
Each Y is independently S or SO ₂ ; or
As a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano.

delete

According to another preferred embodiment of the present invention, the phenolic compound (1) is phenol, cresol, ethyl phenol, butyl phenol, octyl phenol, phenyl phenol, cumylphenol, methoxy phenol, ethoxy phenol, bisphenol A, bisphenol F, bisphenol A and bisphenol A may be any one or more selected from the group consisting of.

According to another preferred embodiment of the present invention, the aldehyde compound is 4: 1 to 20 with respect to the sum of the phenolic compound (1) and the phosphorus-modified phenol compound (2) represented by Formulas 1 to 2 The reaction can be carried out at a molar ratio of 1 :.

According to another preferred embodiment of the present invention, the phosphorus-modified phenolic compound is the phosphorus-modified phenolic compound may be a phosphorus-modified phenolic body of OH monovalent or more. More specifically, phosphorus modified phenol, phosphorus modified cresol, phosphorus modified ethylphenol, phosphorus modified bethylphenol, phosphorus modified octylphenol, phosphorus modified phenyl phenol, phosphorus modified cumylphenol, phosphorus modified methoxy phenol It may be at least one selected from the group consisting of phosphorus modified ethoxy phenol, phosphorus modified bisphenol A, phosphorus modified bisphenol F, phosphorus modified bisphenol A and phosphorus modified bisphenol A.

According to another preferred embodiment of the present invention, the acid catalyst may be any one or more selected from the group consisting of oxalic acid, p-toluene sulfonic acid, M-sulfonic acid, aqueous hydrochloric acid, aqueous sulfuric acid solution, aqueous nitric acid solution and aqueous phosphoric acid solution.

According to another preferred embodiment of the present invention, the aldehyde-based compound may be any one or more of the compounds represented by the following formula 5-6.

[Chemical Formula 5]

[Formula 6]

X는 각각 독립적으로 H 이거나; 또는

Each X is independently H; or

As a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano.

According to another preferred embodiment of the present invention, the phosphorus-modified flame-retardant prepared by the above production method may be any one or more of the compounds represented by the following formula (7).

Resin composition comprising a phosphorus-modified flame-retardant curing agent excellent in UV shielding performance of any one or more of the compounds represented by the formula (7-8).

[Formula 7]

[Formula 8]

화학식 7, 8에서 A는 각각 독립적으로

,

,

또는

로서, 상기 A 중 적어도 하나 이상이

또는

이고,
R₁은 각각 독립적으로

,

또는

이고,
R₂ 및 R₃는 각각 독립적으로 H, 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 또는 시아노이거나; 또는
치환 또는 비치환된 C₁ ~ C₁₀의 알킬, 치환 또는 비치환된 C₁ ~ C₁₀의 알케닐, 치환 또는 비치환 C₁ ~ C₁₀의 알키닐, 또는 치환 또는 비치환된 C₁ ~ C₁₀의 방향족 화합물, 치환 또는 비치환된 C₁ ~ C₁₀의 아실, 치환 또는 비치환된 C₁ ~ C₁₀의 헤테로 알킬이고, 상기 치환은 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 및 시아노 중 어느 하나 이상에 의한 것이고;
X는 각각 독립적으로 H 이거나; 또는
치환 또는 비치환된 C₁ ~ C₁₀의 알킬기로서, 상기 치환은 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 및 시아노 중 어느 하나 이상에 의한 것이고;
Y는 각각 독립적으로 S 또는 SO₂ 이거나; 또는
치환 또는 비치환된 C₁ ~ C₁₀의 알킬기로서, 상기 치환은 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 및 시아노 중 어느 하나 이상에 의한 것이고;
n은 각각 독립적으로 1 ~ 2의 정수; 및 m은 각각 독립적으로 A 부분이 공유결합하고 있는 탄소원자의 원자가를 충족시키는 0 내지 1 중 어느 하나의 정수이다.
본 발명의 바람직한 또 다른 일실시예에 따르면, 상기 UV 차폐 성능이 우수한 인 개질된 난연 경화제의 인 함량이 1 ~ 15%일 수 있다.

In Formula 7, 8 each independently

,

,

or

At least one of A

or

ego,
R ₁ is each independently

,

or

ego,
R ₂ and R ₃ are each independently H, alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, or cyano; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl, substituted or unsubstituted C ₁ to C ₁₀ alkenyl, substituted or unsubstituted C ₁ to C ₁₀ alkynyl, or substituted or unsubstituted C ₁ to C ₁₀ aromatic compounds, substituted or unsubstituted C ₁ to C ₁₀ acyl, substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl, the substitution being alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy , Thiol, and cyano;
Each X is independently H; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl group, wherein the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano;
Each Y is independently S or SO ₂ ; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl group, wherein the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano;
n is each independently an integer of 1 to 2; And m are each independently an integer of 0 to 1 satisfying the valence of the carbon atom to which the A moiety is covalently bonded.
According to another preferred embodiment of the present invention, the phosphorus content of the phosphorus modified flame retardant curing agent excellent in the UV shielding performance may be 1 to 15%.

delete

delete

delete

delete

delete

delete

delete

In order to solve the second problem, it provides a resin composition comprising a phosphorus-modified flame retardant curing agent excellent in any one or more UV shielding performance of the novel compounds represented by the formula (7).

According to a preferred embodiment of the present invention, the flame retardant curing agent may be 10 to 50% by weight relative to 100% by weight of the total resin composition.

According to another preferred embodiment of the present invention, the UV shielding efficiency of the resin composition may be 95% or more in the UV region 100 ~ 400 nm.

In order to solve the third problem, it provides a resin composition for a printed circuit board comprising the resin composition of the present invention described above and a printed circuit board comprising the same.

Phosphorus-modified flame-retardant curing agent having a UV shielding performance prepared through the manufacturing method of the present invention can achieve UV shielding performance, excellent flame retardant properties, adhesion, mechanical and chemical properties without containing a halogen compound.

In addition, the phosphorus-modified flame-retardant curing agent prepared through the above-described manufacturing method has excellent flame retardancy, heat resistance and physical and chemical properties as an additive of engineering plastics such as polycarbonate, ABS, HIPS, epoxy resin, cyanate resin and acrylate It can be used as a raw material of resin and a curing agent of epoxy resin. Through this, it can be widely applied to various composite materials, adhesives, coatings, paints such as PCB boards and insulating plates which require excellent flame retardancy and thermal stability as insulation materials of halogen, high reliability electrical and electronic components such as EMC.

1 to 5 is a UV shielding rate graph for a flame retardant curing agent prepared according to a preferred embodiment of the present invention.
6 to 7 are UV shielding rate graphs for flame retardant curing agents prepared according to Comparative Examples 1 and 2, respectively.
8 is a UV shielding rate graph for Phenol Novolac Hardener with OH.EEW 103 g / eq, solid content 55%, softening point 110 ℃.

Hereinafter, the present invention will be described in more detail.

As described above, in order to overcome the disadvantages of the halogen flame-retardant curing agent, the non-halogen-based flame-retardant curing agent disclosed in the prior art has the advantage of reducing the environmental pollution, but not only the flame retardant effect is lowered compared to the halogen-based flame-retardant curing agent, There was a problem of poor physical and chemical properties. In addition, the resin for printed circuit board manufacturing requires UV shielding performance in addition to the flame retardant properties. Most of the raw materials for UV shielding do not contain materials having flame retardant properties (halogen-based, phosphorus, nitrogen, etc.). The flame retardant properties had a disadvantage.

Accordingly, the present invention provides a phosphorus-modified flame-retardant curing agent having a UV shielding performance and excellent flame retardant effect and physical properties compared to the conventional non-halogen-based flame retardant without a halogen, through which a resin containing a phenolic compound When a phosphorus compound (non-halogen series) is added to impart flame retardancy to the flame retardant, flame retardancy may be improved. However, the reactive flame retardant is a type that reacts chemically with functional groups in the molecule, and has a flame retardant effect without being greatly influenced by external conditions, whereas the added flame retardant is simply dispersed or dissolved in the substrate and often lost from the substrate. In addition, the flame retardant properties are inferior to the reactive type. In addition, in the case of the additive-type flame retardant does not participate in the reaction during the curing reaction with epoxy, the glass transition temperature is reduced, the thermal stability is lowered, in particular, the physical and chemical properties such as significantly lower adhesion properties with the material solved the problem.

Accordingly, the present invention provides a flame retardant by performing a novolak reaction with an aldehyde-based compound of an phenol-based compound (1) and at least one phosphorus-modified phenolic compound (2) of the compounds represented by the following Chemical Formulas 1 to 2 under an acid catalyst. To provide a method for producing a phosphorus modified flame retardant curing agent having excellent UV shielding performance, including the step of preparing to seek to solve the above problems.

[Formula 1]

[Formula 2]

상기 화학식 1 ~ 2에서 R₁은 각각 독립적으로

,

또는

이고,
R₂ 및 R₃는 각각 독립적으로 H, 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 또는 시아노이거나; 또는
치환 또는 비치환된 C₁ ~ C₁₀의 알킬, 치환 또는 비치환된 C₁ ~ C₁₀의 알케닐, 치환 또는 비치환 C₁ ~ C₁₀의 알키닐, 또는 치환 또는 비치환된 C₁ ~ C₁₀의 방향족 화합물, 치환 또는 비치환된 C₁ ~ C₁₀의 아실, 치환 또는 비치환된 C₁ ~ C₁₀의 헤테로 알킬이고, 상기 치환은 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 및 시아노 중 어느 하나 이상에 의한 것이고;
X는 각각 독립적으로 H 이거나; 또는
치환 또는 비치환된 C₁ ~ C₁₀의 알킬기로서, 상기 치환은 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 및 시아노 중 어느 하나 이상에 의한 것이고;
Y는 각각 독립적으로 S 또는 SO₂ 이거나; 또는
치환 또는 비치환된 C₁ ~ C₁₀의 알킬기로서, 상기 치환은 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 및 시아노 중 어느 하나 이상에 의한 것이고;

R ₁ in Formulas 1 to 2 are each independently

,

or

ego,
R ₂ and R ₃ are each independently H, alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, or cyano; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl, substituted or unsubstituted C ₁ to C ₁₀ alkenyl, substituted or unsubstituted C ₁ to C ₁₀ alkynyl, or substituted or unsubstituted C ₁ to C ₁₀ aromatic compounds, substituted or unsubstituted C ₁ to C ₁₀ acyl, substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl, the substitution being alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy , Thiol, and cyano;
Each X is independently H; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl group, wherein the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano;
Each Y is independently S or SO ₂ ; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl group, wherein the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano;

n is independently an integer of 1-2.

Specifically, the phosphorus-modified phenolic compound (2) represented by Formulas 1 to 2 may be prepared by reacting a phenolic compound with a phenolic compound, preferably phenol, cresol, ethylphenol, butylphenol, octylphenol At least one phenolic compound selected from the group consisting of phenylphenol, cumylphenol, methoxyphenol, ethoxyphenol, naphthol, bisphenol A, bisphenol F, bisphenol A, bisphenol A, and biphenol is reacted with a phosphorus compound Preferably, the phenolic compound is reacted with an aldehyde compound using an aldehyde compound under an alkali catalyst to prepare an alkoxylated resol compound using an alcohol solvent, and then a phosphorus compound is reacted to remove the alcohol. Phosphorus-modified phenolic compounds may be prepared, but are not limited thereto.

Phosphorus compounds that can be used at this time include 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide (3,4,5,6-Dibenzo-1,2-oxaphosphane-2- oxide) [hereafter referred to as 'DOPO'], dimethyl phosphite (hereinafter referred to as 'DEP') and diphenylphosphine oxide (hereinafter referred to as 'DPO') compound selected from the group consisting of This use is advantageous for improving UV shielding performance and flame retardant effect and physical properties.

The phosphorus-modified compound (2) may be used without limitation as long as it is a compound represented by Chemical Formulas 1 to 2 above. Preferably, the phenolic compound represented by Chemical Formula 1 may be phosphorus-modified phenol or phosphorus-modified cresol. As the phenolic compound represented by Formula 2, phosphorus-modified bisphenol A, phosphorus-modified bisphenol F, phosphorus-modified bisphenol AD, phosphorus-modified bisphenol S, and the like may be used.

According to a preferred embodiment of the present invention, the phenolic compound (1) may be any one or more of the compounds represented by the following formula (3).

(3)

[Formula 4]

X in Formulas 3 to 4 are each independently H; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl group, wherein the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano;
Each Y is independently S or SO ₂ ; or
As a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano.

delete

According to another preferred embodiment of the present invention, the phenolic compound (1) is phenol, cresol, ethyl phenol, butyl phenol, octyl phenol, phenyl phenol, cumylphenol, methoxy phenol, ethoxy phenol, naphthol, bisphenol It may be any one or more selected from the group consisting of bisphenol F, bisphenol A and bisphenol A, more preferably phenol, cresol can be used as the phenolic compound represented by the formula (3), represented by the formula (4) Use of bisphenol A, bisphenol F, bisphenol AD, bisphenol A, etc. as the phenolic compound is advantageous for improving the UV shielding effect flame retardancy and physical properties.

Meanwhile, in the present invention, both of the phenolic compound (1) and the phosphorus-modified phenolic compound (2) represented by any one or more of Chemical Formulas 1 and 2 may be used to achieve the object of the present invention. If a novolak reaction is carried out by adding a phosphorus compound to the phenolic compound (1) without adding the phosphorus-modified phenolic compound (2), a compound having flame retardant properties may be present in the compound itself. It may not contain any flame retardant properties. In other words, in order to provide the flame retardancy, adhesion, high glass transition temperature, heat resistance, and UV shielding performance, which are required properties of a resin composition for a printed circuit board requiring UV shielding performance, an epoxy resin and a UV shielding epoxy are applied to the resin composition for a printed circuit board. Resin, phosphorus modified epoxy resin or additive phosphorus flame retardant and novolac curing agent are used. However, in case of addition type phosphorus-based flame retardant used to impart flame retardancy, physical and chemical properties such as glass transition temperature decreases, thermal stability is poor, especially adhesion property with material is poor because it does not participate in the reaction during curing with epoxy. The disadvantage of this dropping problem is that when using a modified epoxy resin, the glass transition temperature, thermal stability and adhesive properties are poor due to the reduced curing density of the cured product itself. A separate UV shielding epoxy resin should be added, but the UV shielding epoxy resin does not contain a material exhibiting flame retardant properties, and as a result, a phosphorus content of the cured resin for a printed circuit board is lowered, resulting in a lower flame retardant property. In other words, since two or more substances must be added to impart UV shielding effect and flame retardant properties, the price competitiveness is lowered due to an increase in manufacturing process cost.

In addition, when novolak reaction is performed with an aldehyde-based compound under an acid catalyst using only a phosphorus-modified phenolic compound (2) without the use of a phenolic compound (1), During the reaction, the molecular weight of the reactant may increase rapidly, which may cause a problem that smooth production of the product is impossible. In addition, when the curing reaction with epoxy using a large molecular weight UV shielding flame retardant curing agent due to the large molecular weight UV shielding flame retardant hardening reaction does not occur smoothly due to steric hindrance during the curing reaction, and thus unreacted epoxy and curing agent Substances may remain, resulting in poor physical properties such as glass transition temperature, flame resistance and adhesion of the cured product.

The aldehyde compound that can be used in the present invention is used in the novolak reaction with the phenolic compound and the phosphorus-modified phenolic compound to give UV shielding performance in order to impart UV shielding performance of at least 4 moles of phenolic and phosphorus As long as it can react with the modified phenolic compound, it can be used without limitation, and preferably, an aldehyde compound represented by the following Chemical Formulas 5 and 6 can be used, and more preferably glyoxal, terephthalaldehyde, or the like can be used. .

[Chemical Formula 5]

[Formula 6]

Each of X in Formula 6 is independently H; or
As a substituted or unsubstituted C ₁ to C ₁₀ alkyl group, the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano.

The acid catalyst is not limited as long as it is an acid catalyst used for the novolac reaction of a phenol compound, a phosphorus-modified phenol compound, and an aldehyde compound, and preferably, oxalic acid, PTSA, MSA, ESA, sulfuric acid, nitric acid, hydrochloric acid. In addition to these, p-toluene sulfonic acid, M-sulfonic acid, aqueous hydrochloric acid, aqueous sulfuric acid, aqueous nitric acid and phosphoric acid may be used, as well as existing commercially available acid catalysts.

According to one feature of the invention, any one or more of the compounds represented by the formula (1) to the phenolic compound (1) of any one or more of the compounds represented by the formula (3) to (4) modified phenolic compound (2) Is added and the novolak reaction is carried out with an aldehyde compound under an acid catalyst. At this time, the reaction conditions may preferably be reacted with an aldehyde compound at a molar ratio of 4: 1 to 20: 1 based on the sum (2) of the phenolic compound (1) and the phosphorus-modified phenolic compound. If the reaction molar ratio is out of the range above 4 mol or less may cause gelation problems due to the rapid reaction of the phenolic compound and the aldehyde-based compound, if more than 20 mol, stable production of modified flame-retardant curing agent UV-shielding Although possible, excessive excess phenolic compounds may cause a problem that the productivity of the product is significantly reduced.

The novolak reaction may be performed at 50 to 150 ° C., preferably at 80 to 130 ° C., for 1 hour to 20 hours. The phosphorus content of the phosphorus modified flame retardant curing agent having excellent final UV shielding performance can be adjusted according to the molar ratio of the phosphorus modified phenolic compound of Chemical Formulas 1 to 2 above. Silver may be 1 to 15%, preferably 2 to 10%. If the phosphorus content is less than 1%, the flame retardant effect is insignificant, and if it exceeds 15%, there is a problem in that chemical modification is impossible. UV shielding effects are also typically used to perform quality control of laminates through automatic optical inspection (AOI) in electronic applications such as high density multilayer printed circuit boards. AOIs typically range in wavelength from 450 nm to about 650 nm. This is done by measuring the ultraviolet (UV) absorbance, which can be measured using a UV-Vis meter.

On the other hand, preferably, the phosphorus-modified flame-retardant curing agent compound having excellent UV shielding performance can be obtained through the novolac reaction of the phenolic compound and phosphorus-modified phenolic compound with an aldehyde compound and an acid catalyst rather than an excess of phenolic compound And / or phosphorylated phenolic compounds may be removed via distillation. In addition, the acid catalyst used for the novolak reaction in the present invention is an alkali compound NaOH, KOH, NA ₂ CO ₃ other than oxalic acid separated by heat Using an aqueous solution, such as may be performed to remove the residual acid catalyst through neutralization and a plurality of washing steps, but is not limited thereto, and may be separated through various methods.

According to a preferred embodiment of the present invention, the phosphorus-modified flame-retardant prepared through the novolak reaction may be any one or more of the compounds represented by the following formula (7).

[Formula 7]

[Formula 8]

화학식 7, 8에서 A는 각각 독립적으로

,

,

또는

로서, 상기 A 중 적어도 하나 이상이

또는

이고,
R₁은 각각 독립적으로

,

또는

이고,
R₂ 및 R₃는 각각 독립적으로 H, 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 또는 시아노이거나; 또는
치환 또는 비치환된 C₁ ~ C₁₀의 알킬, 치환 또는 비치환된 C₁ ~ C₁₀의 알케닐, 치환 또는 비치환 C₁ ~ C₁₀의 알키닐, 또는 치환 또는 비치환된 C₁ ~ C₁₀의 방향족 화합물, 치환 또는 비치환된 C₁ ~ C₁₀의 아실, 치환 또는 비치환된 C₁ ~ C₁₀의 헤테로 알킬이고, 상기 치환은 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 및 시아노 중 어느 하나 이상에 의한 것이고;
X는 각각 독립적으로 H 이거나; 또는
치환 또는 비치환된 C₁ ~ C₁₀의 알킬기로서, 상기 치환은 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 및 시아노 중 어느 하나 이상에 의한 것이고;
Y는 각각 독립적으로 S 또는 SO₂ 이거나; 또는
치환 또는 비치환된 C₁ ~ C₁₀의 알킬기로서, 상기 치환은 알콜, 알콕시, 에테르, 에스테르, 케톤, 카르복시, 히드록시, 티올, 및 시아노 중 어느 하나 이상에 의한 것이고;
n은 각각 독립적으로 1 ~ 2의 정수; 및

In Formula 7, 8 each independently

,

,

or

At least one of A

or

ego,
R ₁ is each independently

,

or

ego,
R ₂ and R ₃ are each independently H, alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, or cyano; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl, substituted or unsubstituted C ₁ to C ₁₀ alkenyl, substituted or unsubstituted C ₁ to C ₁₀ alkynyl, or substituted or unsubstituted C ₁ to C ₁₀ aromatic compounds, substituted or unsubstituted C ₁ to C ₁₀ acyl, substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl, the substitution being alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy , Thiol, and cyano;
Each X is independently H; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl group, wherein the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano;
Each Y is independently S or SO ₂ ; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl group, wherein the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano;
n is each independently an integer of 1 to 2; And

m is each independently an integer of 0 to 1 satisfying the valence of the carbon atom to which the A moiety is covalently bonded.

delete

In order to solve the second problem, it provides a resin composition comprising a phosphorus-modified flame retardant curing agent excellent in any one or more UV shielding performance of the novel compounds represented by the formula (7).

Phosphorus-modified flame-retardant curing agent excellent in UV shielding performance of the present invention prepared by the above-described method is 0.1 to 50% by weight of the flame-retardant curing agent with respect to 100% by weight of the resin component in consideration of the balance between mechanical properties and flame retardant performance improvement Crab can be added in an amount of 10 to 30% by weight. In this case, in order to impart excellent flame retardancy, heat resistance and physical and chemical properties as a curing agent, it can be used as a raw material of epoxy resins, cyanate resins and acrylate resins and as a curing agent of epoxy resins. Through this, it can be widely applied to various composite materials such as PCB boards and insulation plates, adhesives, coating agents, paints, etc. which require excellent flame retardancy and thermal stability as insulation materials and halogen-free compounds of high reliability electrical and electronic components. Particularly in electronic applications such as high density multilayer printed circuit boards, it can be usefully used for quality control of laminates through automatic optical inspection (AOI).

Meanwhile, according to a preferred aspect of the present invention, the resin composition including the flame retardant curing agent may include a common epoxy or a curing agent, an inorganic material, a catalyst, or the like alone or in combination. Specifically, the added epoxy may be used without limitation as long as it can be included in a resin composition that is commonly used in printed circuit boards, preferably, bisphenol-A epoxy, bisphenol F-type epoxy, bisphenol A-D epoxy, bisphenol A-type epoxy , Biphenol type epoxy, phenol novolak type epoxy, dicipidi epoxy type, bisphenol e novolak type epoxy, bisphenol f novolak type epoxy, cresol novolak type epoxy, bisphenol esnovolak type epoxy, biphenol novolak type epoxy It may be any one or more selected from the group of xylol novolak-type epoxy, discipidiphenol phenol novolak-type epoxy, biphenol phenyl novolak-type epoxy, tris phenyl phenol novolak-type epoxy group.

According to another preferred embodiment of the present invention, the curing agent constituting the resin composition can be used without limitation as long as it can be included in the resin composition that is commonly used in printed circuit boards, phenol novolak type curing agent, cresol novolak type Curing agent, bisphenol F novolak type hardener, bisphenol A novolak type hardener, bisphenol A novolak type hardener, xylox novolak type hardener, discipidiphenol phenol novolak type hardener, biphenol phenyl novolak type hardener, tris phenyl phenol no Any one or more selected from the group of volacic curing agents and dicyandiamide can be used.

       According to another preferred embodiment of the present invention, the inorganic materials included in the resin composition can be used without limitation as long as it can be included in the resin composition used in a printed circuit board, etc., any one selected from the group of aluminum hydroxide, silica It may be abnormal.

According to another preferred embodiment of the present invention, the catalysts constituting the resin composition can be used without limitation as long as it can be included in the resin composition used for printed circuit boards, etc., specifically 2-methyl as an imidazole catalyst Imidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 -Benzyl-2-methylimidazole, 2-aminoethyl-2-methyl imidazole, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethyl oxy methyl) imidazole or the like alone or mixed May be used but is not limited thereto.

According to another preferred embodiment of the present invention, the UV shielding efficiency of the resin composition may be 95% or more in the UV region 100 ~ 400 nm.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are not intended to limit the scope of the present invention, which will be construed as to help the understanding of the present invention.

<Manufacture example 1>

Into a phenol 94.11 g (1 mole), paraformaldehyde 90.32 (1.25 mole), water 30 g, and sodium hydroxide aqueous solution 3.3 g were added to a reaction tank, and the mixture was heated and stirred for 5 hours at a temperature of 50 ° C., followed by water 41.5 g and sulfuric acid 0.1 Neutralization reaction was carried out using 1.67 g of N sulfuric acid, and then 255 g of methanol was added thereto, followed by reaction at 70 ° C. for 5 hours, and then DOPO 207.36 g was added thereto. After the reaction was carried out for 10 hours or more at a temperature of 140 ℃ removing methanol to prepare a phosphorus-modified DOPO-Phenol.

Hereinafter, DOPO-bisphenol-A and DPO-phenol were also prepared using the above method.

&Lt; Example 1 >

Phenol 564.66 g (6 mole) and DOPO-Phenol 323.11 g (1 mole) were added to the reactor, and DOPO-Phenol was dissolved at 90 ° C while heating and stirring. Then, 8.87 g of an acid catalyst oxalic acid was added three times. Proceeded. Thereafter, 145 g (1 mole) of Glyoxal (40% aqueous solution) was divided into five portions. Thereafter, the reaction was performed at a temperature of 90 ° C. for 6 hours, and then further reaction was performed at 150 ° C. for 1 hour to decompose an acid catalyst, oxalic acid. At 200 ° C to remove unreacted phenol After the phenol recovery process under vacuum, 517 g of a phosphorus modified flame retardant compound having excellent UV shielding performance with a phosphorus content of 5.68% was obtained. (FT-IR results: Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic))

In order to evaluate the UV shielding properties of the curing agent compound was measured using a UV-Vis meter and the results are shown in Figure 1 below.

<Example 2>

Phenol 564.66 g (6 mole) and DOPO-Phenol (P = 9.59%) 646.21 g (2 mole) were added to the reactor and dissolved DOPO-Phenol at a temperature of 90 ° C. under heating and stirring, followed by 12.1 g of acid catalyst oxalic acid three times. Injected over. Thereafter, 145 g (1 mole) of Glyoxal (40% aqueous solution) was divided into five portions. After the reaction for 6 hours at 90 ℃ temperature for 1 hour further reaction at 150 ℃ to decompose the acid catalyst oxalic acid and then proceed with the phenol recovery process at 200 ℃ to remove the unreacted phenol after phosphorus content of 8.73% 646 g of a modified modified flame retardant curing agent compound having excellent UV shielding performance was obtained. (FT-IR results: Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic))

In order to evaluate the UV shielding properties of the curing agent compound was measured using a UV-Vis meter and the results are shown in Figure 2 below.

<Example 3>

564.66 g (6 moles) of phenol and 680 g (1 mole) of DOPO-bisphenol-A (P = 9.4%) were added to the reactor, and dissolved DOPO-bisphenol-A at 90 ° C while stirring under heating. It was injected three times. Thereafter, 145 g (1 mole) of Glyoxal (40% aqueous solution) was divided into five portions. After the reaction for 6 hours at a temperature of 90 ℃ and then further reaction for 1 hour at 150 ℃ to decompose the acid catalyst oxalic acid and then proceed with the phenol recovery process at 200 ℃ to remove the unreacted phenol after phosphorus content of 7.0% 858 g of a modified modified flame retardant curing agent compound having excellent UV shielding performance was obtained. (FT-IR results: Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic))

In order to evaluate the UV shielding properties of the curing agent compound was measured using a UV-Vis meter and the results are shown in Figure 3 below.

<Example 4>

Phenol 564.66 g (6 mole) and DPO-Phenol (P = 10%) 310 g (1 mole) were added to the reactor and dissolved in DPO-Phenol at a temperature of 90 DEG C while heating and stirring. Injected over. Thereafter, 145 g (1 mole) of Glyoxal (40% aqueous solution) was divided into five portions. After the reaction for 6-7 hours at a temperature of 90 ℃ and then further reaction at 150 ℃ for 1 hour to decompose the acid catalyst oxalic acid and then proceed with a phenol recovery process at 200 ℃ to remove the unreacted phenol phosphorus content 5.71 515 g of a modified modified flame retardant curing agent compound having good UV shielding performance of% was obtained. (FT-IR results: Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic))

In order to evaluate the UV shielding properties of the curing agent compound was measured using a UV-Vis meter and the results are shown in Figure 4 below.

<Example 5>

Phenol 564.66 g (6 mole) and DOPO-Phenol (P = 9.59%) 323.11 g (1 mole) were added to the reactor and dissolved DOPO-Phenol at a temperature of 90 ° C. while heating and stirring. Injected over. Thereafter, 264 g (1 mole) of P-Terephthalaldehyde 50% Soluion (Tolunen) was divided into 2 hours, and the reaction was performed. After the reaction for 6-7 hours at a temperature of 90 ℃ and then further reaction at 150 ℃ for 1 hour to decompose the acid catalyst oxalic acid, and then proceed with a phenol recovery process at 200 ℃ to remove the unreacted phenol phosphorus content 4.9 568 g of a modified flame retardant curing agent compound having good UV shielding performance of% was obtained. (FT-IR results: Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic))

In order to evaluate the UV shielding properties of the curing agent compound was measured using a UV-Vis meter and the results are shown in Figure 5 below.

Comparative Example 1

655 g of a flame retardant compound having a phosphorus content of 4.36% in the same manner as in Example 1 except that 326 g of triphenylphosphate (phosphorus content of 9.5%, C ₁₈ O ₄ PH ₁₅ ) was added as a phosphorus compound instead of DOPO-Phenol Obtained.

In order to evaluate the UV shielding properties of the curing agent compound was measured using a UV-Vis meter and the results are shown in Figure 6 below.

Comparative Example 2

Methyl Cellosolve and DOPO-Phenol (P = 9.59%) 323.11 g (1 mole) were added to the reactor and dissolved DOPO-Phenol at a temperature of 90 ° C. while heating and stirring. Thereafter, 3.23 g of an acid catalyst oxalic acid were added three times, and 36.25 g of Glyoxal (40% aqueous solution) was divided and added over 2 hours to proceed with the reaction. After the reaction for 10 hours at 90 ℃ temperature to remove the acid catalyst oxalic acid to remove Methyl Cellosolve at 150 ℃ for 1 hour after the addition of Methyl Cellosolve after removal of the phosphorus content of 9.1% UV shielding performance is excellent 330 g of prepared flame retardant curing agent compound were obtained. (FT-IR results: Phenol-like hydroxy group: 3300㎝ -1, P = O: 1200㎝ -1 / 1280㎝ -1, PCO (Aromatic): 972 ㎝ -1, 1424 ㎝ -1 PC (Aromatic))

In order to evaluate the UV shielding properties of the curing agent compound was measured using a UV-Vis meter and the results are shown in Figure 7 below.

On the other hand, Figure 8 shows the measurement results using a UV Vis meter of Phenol Novolac Hardener OH EEW 103g / OH, 55% solids, 110 ℃ softening point.

<Evaluation Example>

Examples 1 to 5 and Comparative Examples 1 to 2 prepared by the flame-retardant compound prepared in a compounding ratio as shown in Table 1 in a conventional manner to prepare an adhesive for a printed circuit board.

In addition, in order to evaluate the physical properties of the phosphorus-modified flame-retardant curing agent compounds prepared in the above Examples and Comparative Examples was performed as shown in Table 1 above to show the results.

Specifically, the resin was prepared in Examples and Comparative Examples at the mixing ratio shown in Table 1 to prepare a varnish, and then impregnated with glass fibers to perform a prepreg operation. Prepreg (prepreg) was pressed to proceed at 175 for 5 minutes by applying a semi-cured state 15 minutes after pressing the back 120 minutes 40kgf / cm ² pressure to 25kgf / cm ² pressure for specimens of 8-fold at 190 after a. After cooling for 30 minutes with a refrigerant.

(1) The flame retardancy test was performed by the UL-94 method.

Specifically, the specimen is made by using 5 “× 1/2” and 5 specimens to contact the specimen for 10 seconds, and then remove the flame, turn off the light, and then contact it again for 10 seconds to remove the flame again. The sum of the first and second burn times of the open specimens was calculated. (Flame retardant rating is V-0 when the sum of 1st and 2nd combustion time is within 50 seconds, V-1 when more than 50 seconds-less than 250 seconds)

(2) Glass transition temperature measurement experiment was performed using differential thermal analyzer (DSC). (20 / min)

(3) Peel strength was measured by GIS C-6471 method.

     (4) UV shielding evaluation was measured using SINCO S-3100 equipment.

      (5) The gelation time was measured at 170 ° C using a gel time machine.

(6) The UV shielding rate was measured using a UV-Vis meter as the blending ratio shown in the above table, and the average UV shielding rate at 100 to 400 nm is shown in Table 1.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 99.4% 99.5% 99.6% 99.5% 99.3% 99.1% 67.5%

Resin composition 1
(Example 1) Resin composition 2
Example 2 Resin composition 3
(Example 3) YD-011M68 14.7 14.7 14.7 YDPN-638A80 112.5 112.5 112.5 Modified epoxy 0 0 0 KDT-4400 0 0 0 Flame Retardant (Example 1 ~ Comparative Example 2) (NV 60%) 131.3 87.26 114.5 Phenol Novolac Hardener 0 53.54 41.63 Dicy 2 2 2 Silica 44.69 45.45 47.9 MCs 44.69 45.45 47.9 2MI 0.01 0.01 0.01 Composition UV shielding OK OK OK Flame retardant rating / burn time V-0 (25s) V-0 (23s) V-0 (24 s) Phosphorus content 2.0% 2.0% 2.0% Peel strength 1.4 1.3 1.4 170 gel time 199 s 165 s 175 s Glass transition temperature 155.4 166.82 173.2

Resin composition 4
Example 4 Resin Composition 5
(Example 5) Comparative Resin Composition 1
(Comparative Example 1) Comparative Resin Composition 2
(Comparative Example 2) YD-011M68 14.7 14.7 14.7 14.7 YDPN-638A80 112.5 112.5 112.5 112.5 Modified epoxy 0 0 0 0 KDT-4400 0 0 0 0 Flame Retardant (Example 1 ~ Comparative Example 2) (NV 55%) 131.3 189 141.34 81.33 Phenol Novolac Hardener 0 0 0 56.72 Dicy 2 2 2 2 Silica 44.69 50.98 46.2 45 MCs 44.69 50.98 46.2 45 2MI 0.01 0.01 0.01 0.01 Composition UV shielding OK OK OK OK Flame retardant rating / burn time V-0 (21s) V-0 (45s) V-1 (55s) V-0 (41s) Phosphorus content 2.0% 2.0% 1.6 2.0% Peel strength 1.4 1.3 0.9 1.2 170 gel time 205 195 210 170 Glass transition temperature 157.0 155.0 148.6 150.5

Resin composition 3
(Example 3) Comparative Resin Composition 3
YD-011M68 14.7 0 YDPN-638A80 112.5 0 Modified epoxy 0 135.71 KDT-4400 0 7.14 Flame Retardant (Example 1 ~ Comparative Example 2) (NV 60%) 114.5 0 Phenol Novolac Hardener 41.63 52.35 Dicy 2 2 Silica 47.9 52.35 MCs 47.9 52.35 2MI 0.01 0.01 Composition UV shielding OK OK Flammability V-0 V-0 Phosphorus content 2.0% 2.0% Peel strength 1.4 1.0 170 gel time 175 s 153 Glass transition temperature 173.2 125

1 to 8 show the UV shielding performance of the phosphorus-modified flame-retardant curing agent prepared in accordance with the present invention and the comparative example, the x-axis shows the wavelength of light and the y-axis shows the light transmittance. It can be seen from the graphs of FIGS. 1 to 8 that the shielding effect of light in the wavelength range of the light can be seen. It can be seen that the transmittance in the wavelength range is close to 100, and there is no shielding effect, and the closer to 0, the better the shielding effect at the wavelength. It can be seen that the UV transmittance at 390 nm is 0%.

1 to 8 and Table 1, it can be seen that the UV shielding rate of the flame retardant of Examples 1 to 5 of the present invention is superior to the UV shielding effect compared to Comparative Examples 1 and 2. In addition, as shown in Tables 2 and 3, resin plastics 1 to 4 using the flame retardant of Examples 1 to 5 contained UV-shielding effect and reactive type of flame retardant, compared to Comparative resin composition 1 containing additive flame retardant. It can be seen that the adhesion is excellent, the glass transition temperature is high, and the flame retardancy is excellent.

In addition, as can be seen in Table 4, when using the resin using an embodiment of the present invention has a phosphorus and UV shielding performance exhibiting the flame retardant properties of the resin itself, separate flame retardant epoxy (phosphorus epoxy) and UV when preparing the resin composition It can be seen that the performance is exhibited without the addition of epoxy resin (KDT-4400, Kukdo Chemical Co., Ltd.) having shielding performance. Specifically, when the flame retardant epoxy is added as shown in the results of Table 4, it can be seen that the glass transition temperature and adhesion strength is significantly reduced.

Phosphorus-modified flame-retardant curing agent and a resin composition comprising the same excellent in the UV shielding performance produced by the manufacturing method of the present invention can be widely applied to various composite materials, such as PCB substrates and insulating plates, adhesives, coating agents, paints.

Claims (13)

delete delete delete delete delete delete delete delete Resin composition comprising a phosphorus-modified flame-retardant curing agent excellent in UV shielding performance of any one or more of the compounds represented by the formula (7-8).
[Formula 7]

[Chemical Formula 8]

In Formula 7, 8 each independently

,

,

or

At least one of A

or

ego,
R ₁ is each independently

,

or

ego,
R ₂ and R ₃ are each independently H, alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, or cyano; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl, substituted or unsubstituted C ₁ to C ₁₀ alkenyl, substituted or unsubstituted C ₁ to C ₁₀ alkynyl, substituted or unsubstituted C ₁ to C ₁₀ Aromatic compounds, substituted or unsubstituted C ₁ to C ₁₀ acyl or substituted or unsubstituted C ₁ to C ₁₀ heteroalkyl, the substitution being alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, By at least one of thiol, and cyano;

Each X is independently H; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl group, wherein the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano;

Each Y is independently S or SO ₂ ; or
Substituted or unsubstituted C ₁ to C ₁₀ alkyl group, wherein the substitution is by at least one of alcohol, alkoxy, ether, ester, ketone, carboxy, hydroxy, thiol, and cyano;

n is each independently an integer of 1 to 2; And
m is each independently an integer of 0 to 1 satisfying the valence of the carbon atom to which the A moiety is covalently bonded. 10. The method of claim 9,
The resin composition, characterized in that 10 to 50% by weight of the flame-retardant curing agent relative to 100% by weight of the total resin composition. 10. The method of claim 9,
UV shielding efficiency of the resin composition is a resin composition, characterized in that more than 95% in the UV region 100 ~ 400 nm. A resin composition for a printed circuit board comprising the resin composition of any one of claims 9 to 11. A printed circuit board comprising the resin composition of claim 12.

Images