TW201144414A - Manufacturing method of flame retardant and phosphorous-modified hardener - Google Patents

Abstract

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. 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 to 400 nm.

Description

201144414 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a phosphorus-modified flame retardant curing agent excellent in UV shielding performance, and more particularly to an ultraviolet shielding property, and at the same time A method for producing a phosphorus-modified flame retardant curing agent having flame retardancy and heat resistance. [Prior Art] Today, the use of plastics is widely used in various industrial fields such as electric fluorine machines, conveying machines, building materials, etc., but almost all organic substances such as broken, oxygen, hydrogen, etc., continue to increase due to the characteristics of easy combustion. The need for safe flame retardation in the event of a fire. In general, when a fire burns, fuel, oxygen, and energy are required, and when it is impossible to satisfy any of the conditions, the fire cannot occur. That is, in the method of burning the plastic kick, the factor of one or more of the three factors causing the fire can be specifically realized. The flame retardant curing agent refers to a compound having a high flame retardancy effect by chemically or physically adding a halogen-based, a filler, a nitrogen-based or a metal product, and the like, and can be delayed in a polymer material having an easily combustible property. Burns and prevents the burning of substances from expanding. The types and uses of flame retardant curing agents are classified variously, but are mainly classified into reactive and additive types. The reactive flame retardant curing agent refers to a type that has a functional group in the molecule and undergoes a chemical reaction, and is not subject to external strip molding, so that the flame retardant effect continues to be a compound turning agent, and (4) visualizing the physical mixing and addition in the plastic. Disperse is the only one used for thermoplastic plastics. 201144414 Mainly used for thermoplastic plastics. Today's additive or reactive flame retardant curing agents are available in a wide variety of types. As an additive flame retardant curing agent, there are three kinds of sulphuric acid squeegee, sulphur benzene, two base squama, and two base squama. Acid g, tributyl acid acid g, ginseng (dimethyl propyl) phosphate, ginseng (di-propyl) phosphate, etc.; as a reactive flame retardant curing agent, bromophenyl allylic bromophenol The group ether, vinyl gas acetate, decanediol, tetrabromobisphenol A, etc. belong to this. The reactive flame retardant curing agent is chemically reacted with the substrate, so it is always mixed with the polymer structure, but the additive type resisting agent system does not produce chemistry due to the flame retardant substance and the polymer matrix. The reaction, the added flame retardant substance is simply dispersed or dissolved in the matrix, and often is often lost from the matrix. & " y ! and make electricity such as circuit boards.

Application field 'implemented by automatic optical inspection (A management. The application is typically in the range of ~ fine nm ultraviolet light (IAO absorbance, so 'the time to make the ultraviolet light ❺ 赋 赋 赋 赋 赋 赋 — — — — — — — — — — — — — — — — — — — — — — — — — — — , Heart: Mooncake composition, I-based compound' uses Bi type EpGxy, Wei # epoxy resin, secret varnish ring v曰 (_laC Epoxy), tetraphenyl ethane epoxy Resin (T 啲 yl yl yl p 作为 作为 作为 作为 作为 作为 作为 作为 作为 , , , , , , , 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四二印=: 201144414 cy, DDS, DDM, varnish, 曱 秘 清 varnish, double varnish curing agent. The resin used in the manufacture of printed circuit boards must have excellent characteristics, steel or Ming silk Substrates such as yttrium imide films have excellent adhesion, high surface transfer temperature, high dimensional stability, low water absorption and uv shielding properties, but materials with uv shielding properties generally do not contain flame retardant properties (tooth Prime, dish, gas, etc.)罝 There are printed electric secrets (4) _, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ However, the type in which the chemical reaction is carried out in the molecule of the flame retardant's molecule is not greatly affected by external conditions, but the added substance is simply added as compared with the substance exhibiting the flame retardant effect. Dispersed or dissolved in the matrix, and often lost from the matrix, and the flame retardant properties have the disadvantage of lower flame retardancy than the reactive type. And in the case of 'additional flame retardant, via non-participation, epoxy tree _ In the reaction at the time of the reaction, the surface transfer temperature is reduced, and the thermal stability is lowered. In particular, there is a problem that physical and chemical physical properties such as a significant decrease in the subsequent properties of the material are inferior. [Summary of the Invention] [Summary of the Invention] I [The subject to be solved by the present invention] The present invention has been made to solve the aforementioned problems. The problem to be solved by the present invention is to provide a #uv shielding property 201144414 chemistry even if it does not contain a (tetra) compound. A method for producing a flame retardant curing agent having excellent physical properties and excellent physical flame retardancy and H-mechanical physical phosphorus modification. [Means for Solving the Problem] The present invention for achieving the object provides an excellent uv shielding performance. And a method for producing a modified flame retardant curing agent, comprising the squamous compound (2) of any one or more of the compounds represented by the compound (1) and the following chemical formulas 1 to 2; Under the acid catalyst, the step (4) is a step of preparing a flame retardant curing agent by performing a novolac reaction. [Chemical 1]

〔化2〕

r£

In the chemical formulas 1 to 2, the cardiac systems are each independently: 201144414

R^R3 are each independently a hydrazine, an alcohol, a silk group n, a carboxyl group, a hydroxyl group, a thiol or a cyano group, or a Ci~c-shaped filament substituted or _substituted, substituted by a c-heart, a peak Or _substituted cvcJii t substituted or unsubstituted c^c —- off A /, earth or substituted sulfhydryl group, by 枓^ generation and non-beauty, non-peak, peak of Cl~ClG An alkyl group, the substitution may be any one of an alcohol, a methoxy group, a thiophene thiol, and a cyano group; the carboxylate hydroxy X groups are each independently Η; or a substituted or unsubstituted c-wide Cw a calcination group, wherein the substitution may be:, an alcohol, an alkoxy group, a _, a s, a _, a ph, a thiol, a thiol or a nitro group; the Y series are each independently S or so2 Or a substituted or unsubstituted C1~C1Q alkyl group, which may be an alcohol, a methoxy ether, a brew, a sulphur, a thiol, a thiol, a thiol, and a gas group. Each is independently an integer of 丨~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 Chemical Formulas 3 to 4 of 201144414. 〔化3〕

〔化4〕

In the chemical formulas 3 to 4, the X groups are each independently Η; or a substituted or unsubstituted CcCw alkyl group, and the substitution may be an alcohol, an alkoxy group, an ether, an ester, a ketone, a carboxyl group, a hydroxyl group, a thiol. And any one of the cyano groups; the Y series are each independently S or so2; or the substituted or unsubstituted c-C1Q alkyl group, the substitution may be an alcohol, a hospitaloxy group, an ether, an ester, a bright, Any one of a buffer group, a carboxyl group, a thiol group, and a cyano group. According to another preferred embodiment of the present invention, the phenolic compound (1) may be selected from the group consisting of a pro, a test, an ethylene, a Ding, a Xin, a phenyl, an anisine, 201144414 methoxyphenol, Any one or more of the group consisting of ethoxylated phenol, bisphenol A, bisphenol F, bisphenol A, and bisphenol ad. According to another preferred embodiment of the present invention, the phenolic compound and the conjugated compound (2) represented by the chemical formulas 1 to 2 may be 4:1 to 20 with respect to the aldehyde compound: The molar ratio of 1 is reacted. According to another preferred embodiment of the present invention, the phosphorus-modified phenolic compound may be a phosphorus-modified phenol having an OH of 1 or more. More specifically, it may be selected from phosphorus-modified phenol, phosphorus-modified cresol, phosphorus-modified phenol, phosphorus-modified butyl phenol, phosphorus-modified octyl phenol, and phosphorus modified. Phenolic phenol, phosphorus-modified anisidine, phosphorus-modified decyl phenol, phosphorus-modified ethoxylated phenol, phosphorus-modified bisphenol A, phosphorus-modified double Any one of the group consisting of phenol F, phosphorus-modified bisphenol S, and phosphorus-modified bisphenol AD. According to another preferred embodiment of the present invention, the acid catalyst may be selected from the group consisting of oxalic acid, p + ρ Ί 任一 ~ acid, aqueous hydrochloric acid, aqueous sulfuric acid solution, aqueous nitric acid solution and aqueous phosphoric acid solution. The present invention is a further preferred embodiment, and the secret compound may be any one of the compounds represented by the following J to 6. 〔化5〕

〔化6〕 201144414

The X series are each independently Η; or a substituted or unsubstituted CcCio, which may be any of an alcohol, an alkoxy group, an ether, an ester, a ketone, a carboxyl group, a hydroxyl group, a thiol, and a cyano group. the above. According to another preferred embodiment of the present invention, the phosphorus-modified flame retardant curing agent produced by the production method may be any one of the compounds represented by the following Chemical Formulas 7 to 8. A resin composition of a phosphorus-modified flame retardant curing agent having excellent U V shielding properties, which is one or more of the compounds represented by the following Chemical Formulas 7 to 8. [7]

A A

201144414

In Chemical Formulas 7 and 8, the eight systems are each independently: OH

At least one of the above A

OH

〇H

or

OH R

The Ri series are each independently:

Ketones, R2AR3 are each independently H, an alcohol, an alkoxy group, an ether, a carboxylic acid carboxyl group, a hydroxyl group, a thiol or a cyano group; or a mr-substituted or non-(tetra)-substituted alkyl group, a substituted or a non-treated medium. Replaced or not replaced (4). Substituted or unsubstituted Cl~CiQq fragrant compound, ^ substituted C heart county, substituted or unsubstituted 201144414 group, the substitution may be an alcohol, an alkoxy group, an ether, an ester, a ketone, Any one of a carboxyl group, a hydroxyl group, a thiol group and a cyano group; the X groups are each independently a hydrazine; or a substituted or unsubstituted CcCio alkyl group, the substitution may be an alcohol, an alkoxy group, an ether, an ester, Any one of a ketone, a carboxyl group, a hydroxyl group, a thiol group and a cyano group; the Y series are each independently an S or a 2; or a substituted or unsubstituted CfCu) alkyl group, and the substitution may be an alcohol or an alkoxy group. Any one or more of an ether, an ester, a ketone, a carboxyl group, a hydroxyl group, a thiol, and a cyano group; the η series are each independently an integer of 1 to 2; and the m systems are each independently an integer of 0 to 1, such that The valence of the carbon atom that satisfies the covalently bonded moiety. [Effect of the Invention] The phosphorus-modified flame retardant curing agent having UV shielding properties produced by the production method of the present invention can simultaneously achieve UV shielding performance, excellent flame retardant properties, adhesion, and even if it does not contain a halogen compound. Mechanical, chemical properties. Moreover, the phosphorus-modified flame retardant curing agent produced by the production method has excellent flame retardancy, richness, and physical and chemical properties as additives of engineering plastics such as carbonate, ABS, and HIPS, and has It may be used as a raw material for epoxy resins, cyanate resins and acrylate resins, and as a curing agent for epoxy resins. Insulation materials for electrical and electronic components such as EMC, which are highly reliable, can be widely applied to PCB substrates and insulating sheets, etc., which require excellent flame retardancy 12 201144414 and thermal stability. Materials, adhesives, coating agents, coatings, and the like. [Embodiment] [Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in more detail. As mentioned above, in order to overcome the shortcomings of the flame retardant curing agent, in the case of the non-dental flame retardant curing agent disclosed in the prior art, there is an advantage of reducing the environmental pollution, but with the flame retardant curing agent. In comparison, not only the flame retarding effect is low, but also various physical and chemical physical properties are poor. Further, in the case of a resin for producing a printed circuit board, in addition to flame retardant properties, uv shielding performance is required, but almost all materials for UV shielding do not contain flame retardant substances, bismuth, nitrogen, etc. There is a disadvantage that the resin for producing a printed circuit board has poor flame retardancy. /According to the above, the present invention provides a phosphorus-modified resisting agent having a brittle effect, a physical property, and a UV shielding property, even if it does not contain a halogen, compared with the conventional non-dental flame-retardant SHb agent. In order to impart flame retardancy to the resin of the age-containing compound, the addition of the (10) compound (non-dentate type) If-form improves the flame retardancy. However, in the case of the reactive flame retardant, the type which has a g energy group and undergoes a chemical reaction is not greatly affected by the external condition = ring: the flame retardant added is simpler than the substance exhibiting the effect. Disperse or transfer to the substrate, the secret of the loss of the substrate from the substrate. ^ Characteristics and reaction ratio, with the disadvantage of low barrier. And in the case of 'additional flame retardant, the glass transition temperature is reduced and the thermal stability is lowered by not participating in the reaction with the epoxy resin of 13 201144414. In particular, the solution and the subsequent properties of the material are significantly lowered. The problem of physical and chemical properties is poor. According to the present invention, there is provided a method for producing a phosphorus-modified flame retardant curing agent having excellent UV shielding properties, which comprises a phenolic compound (1) and a compound represented by the following Chemical Formulas 1 to 2; The phosphorus-modified phenolic compound (2) is subjected to a novolak reaction under an acid catalyst to produce a flame retardant curing agent, and the above problems are solved.

〔化1〕 QH

〔化2〕

In the chemical formulas 1 to 2, 1^ are each independently: 14 201144414

Ester, brewing} sharp / (10) 3 series are each independently hydrazine, alcohol, methoxy, carboxyl, hydroxy, thiol or cyano; or replaced by rc ^ r replaced by county, peak or non-substituted ^ county , substituted or unsubstituted. a cvc-like aromatic compound substituted by a block, or a Korean or a secret, substituted or not

a hydrazine ketone, a ketone, a hydroxyl group, a hydroxyl group, a substituted thiol group of a substituted CrCio group, a substituted or unsubstituted thiol group, and the substitution may be any one of an alcohol, an alkoxy group, an ether thiol, and a cyano group. The X series are each independently a hydrazine; or an alkoxy group or more; a substituted or unsubstituted lye group of an alkyl group, an ester, a ketone, a carboxyl group, a hydroxyl group, a thiol group, and a cyano group, which is substituted or unsubstituted. The alcohol may be independently s or so2; or substituted or unsubstituted Ci~Ciq alkyl, the substitution may be an alcohol, an alkoxy group, an ether, an ester, a ketone, a carboxyl group, a hydroxyl group, a sulfur Alcohol and cyano oxime ~ .. η are each independently an integer of 丨~2. Specifically, the phosphorus-modified phenolic system represented by the chemical formula 丨2 can be produced by reacting a compound with a compound, preferably from a phenol or a phenol. , Ethylphenol, butyl phenol, octyl phenol, phenyl phenol, indoline, oxime, ethoxy, naphthalene, double age A, double F, bisphenol S, double expectant AD The phenolic compound of any one or more of the group consisting of biphenyl groups is produced by reacting with a constitutive compound, preferably a compound of a desired compound, and a resol resin reaction with a route compound under a base catalyst condition. After the resol phenol resin compound is produced by alkoxylation using an alcohol-based solvent, a phosphorus-modified phenol-based compound is produced by a dealcoholization reaction with a phosphorus-based compound, and the method for producing the phenol-based compound is not limited thereto. At this time, as the phosphorus compound to be used, a compound selected from 3,4,5,6-dibenzo-1,2-oxaphosphonium-2-oxide (3,4,5,6) Dibenzo-l, 2_oxaphosphane -2-oxide) [hereinafter referred to as 'DOPO'], Dimethylphosphite (hereinafter referred to as 4DEP,) and Diphenylphosphine Oxide (hereinafter referred to as ' The compound of the group consisting of Dp〇,] is advantageous for the UV shielding property, the flame retarding effect, and the physical property. The phenolic compound (2) thus modified by the phosphorus is a compound represented by the chemical formula ,~ In the case of the compound represented by the chemical formula 1, it is preferred to use a modified age and a modified intermediate, as a compound represented by the chemical formula 2, Use phosphorus-modified bisphenol A and phosphorus-modified bisphenol? Phosphorous modified bisphenol a D, phosphorus modified bisphenol s, and the like. 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 Chemical Formulas 3 to 4. 201144414 〔化3〕

〔化4〕

In Chemical Formulas 3 to 4, X is each independently Η; or a substituted or unsubstituted Ci-Cn alkyl group, and the substitution may be an alcohol, an alkoxy group, an ether, an ester, a ketone, a thiol group, a thiol group. And any one of a thiol and a cyano group; the Y series are each independently S or so2; or a substituted or unsubstituted CcCio alkyl group, the substitution may be an alcohol, a hospitaloxy group, an ether, an ester, a ketone Any one of above, thiol, thiol, thiol and cyano. According to another preferred embodiment of the present invention, the phenolic compound (1) is selected from the group consisting of phenol, indophenol, ethylphenol, butylphenol, octylphenol, phenylphenol, anisidine, anthoxyphenol, and B. More than or equal to the group consisting of oxyphenol, naphthol, bisphenol A, bisphenol F, bisphenol S and 17 201144414 bisphenol AD, more preferably, as a compound represented by the chemical formula 3, It can be used as the compound of the formula 4, and the use of double expectant A, double expectant F, double AD, and bisphenol is beneficial to the UV shielding performance, the flame retarding effect and the physical property. On the other hand, in the present invention, the phenol-based compound (丨) and the phosphorus-modified phenol-based compound (2) represented by any of the above formulas 1 to 2 are used for the purpose of the invention. If the ruthenium-based compound (7) is not added to the compound (1)+, and the compound is added to the varnish, the nucleus can be viscous, but the compound itself is not flammable. For compounds, there is no problem with flame retardant properties. In the case of the resin composition required for the UV-based (four) printed circuit board, the physical properties required to be imparted are flame retardancy, adhesion, high glass transition temperature, heat resistance and UV shielding performance, and resins for printed circuit boards. As the composition, an epoxy resin, a UV-shielding epoxy resin, a modified epoxy resin, an additive-type dish-based flame retardant, and an acid-preserving varnish curing agent are used. However, in the case where an additive-type phosphorus-based flame retardant is used for imparting flame retardancy, the glass transition temperature is lowered and the heat stability is lowered by not participating in the reaction with the epoxy group hardening reaction, and in particular, the material and the material are generated. Then, the characteristics are remarkably reduced, and the physical properties of the physical properties are poor. The use of the bowl-modified epoxy tree has the effect of reducing the hardening density of the cured product itself, reducing the glass transition temperature, and the heat. The disadvantage of the decrease in stability and the difference in the subsequent characteristics is that it is necessary to add another 17% shielding epoxy resin without UV shielding performance, but the shielding epoxy resin does not contain a substance exhibiting flame retardant properties, and as a result, it has a resin for a printed circuit board. The scale of the hardened material is low and the flame retardant property is deteriorated. In other words, in order to impart 1; 乂 shielding effect and flame retardant property, it is necessary to add two or more kinds of substances, which has the disadvantage that the cost of manufacturing engineering increases and the price competitiveness is low. Further, when the phenolic compound (1) is not used, only the phenolic compound (2) which is filled with the modified phenolic compound is subjected to a novolak reaction with an aldehyde-based compound under an acid catalyst, and is subjected to a phosphorus-modified phenolic system. When the relative large molecular weight is reacted in the novolac reaction, the molecular weight of the reactants is drastically increased, and there is a problem that the product can be produced smoothly. Moreover, in the case of using a large molecular weight 1} 乂 masking flame retardant curing agent in the epoxy group hardening reaction, when the reaction is hardened by a UV shielding flame retardant curing agent having a large molecular weight, the hardening reaction cannot be smooth due to steric hindrance As a result, the unreacted substances of the epoxy group and the curing agent remain, and the problem of deterioration of the glass transition temperature, flame resistance, and subsequent physical properties of the cured product occurs. The aldehyde compound used in the present invention is used in the reaction of the phenolic compound and the dish-modified phenolic compound in a novolak reaction, and is a TUV shielding property, and if 1 mol of the aldehyde compound can be used with 4 mol. In the case of the above phenol-based or phosphorus-modified compound, the aldehyde-based compound represented by the following Chemical Formulas 5 to 6 can be preferably used, and it is more preferred to use glyoxal. , p-benzoaldehyde, and the like. 〔化5〕 & f

H W [化6] 201144414

Η X In Chemical Formula 6, X is each independently η; or a substituted or unsubstituted alkyl group of C1 to C1Q, and the substituted hydrazine is an alcohol, an alkoxy group, an ether, an ester, a ketone, a carboxyl group, a hydroxyl group, or a sulfur. Any one of an alcohol and a cyano group. The acid catalyst is not limited as long as it is an acid catalyst used in a varnishing reaction between a phenolic compound and a phenolic compound and an acid compound, and preferably contains oxalic acid, PTSA, MSA, ESA, A conventional acid catalyst which is scaled from the surface of the crucible may be used in addition to sulfuric acid, terminal acid, hydrochloric acid, p-toluene acid, a continuous acid, an aqueous hydrochloric acid solution, a sulfuric acid aqueous solution, an aqueous nitric acid solution, and an aqueous phosphoric acid solution. According to one of the features of the present invention, the compound (1) of any one of the compounds represented by the chemical formulas 3 to 4 and the phosphorus-modified phenolic compound (2) represented by the chemical formulas 1 to 2 are added. One or more phenolic compounds are subjected to a novolak reaction with an aldehyde compound under an acid catalyst. In this case, the reaction conditions are preferably based on the sum of the phenolic compound (1) and the disc-modified lanthanide compound (2), which can be compared with the acid bismuth compound by a molar ratio of 4:1 to 2:1. reaction. If the reaction molar ratio is outside the above range, in the case of 4 mol or less, since the phenolic compound reacts violently with the aldehyde compound, there is a problem that the possibility of gelation occurs, and in the case of 2 mol or more, There is a possibility of stable production of 11 乂 shielded phosphorus-modified flame retardant curing agent, but due to the above excess phenolic compound, the problem of the product's productivity is significantly low. 20 201144414 The phenolic varnish reaction is based on 50 It is carried out at ~150 ° C, preferably 80 to 13 〇 y L for 1 hour to 20 hours. The phosphorous content of the phosphorus-modified sulphuric acid, which is excellent in UV shielding performance, can be adjusted by the molar ratio of the phosphorus-modified ageing compound of the chemical formula 1 to 2, and the phosphorus content of the final compound, uv Excellent shielding performance σ The phosphorous-modified flame retardant curing agent may have a phosphorus content of 1 to 15%, preferably %. If the phosphorus content is less than 1%, the flame retarding effect is small, and if it exceeds 15%, there is a problem that chemical structural modification is impossible. Moreover, in general, in the field of electronic applications such as high-density multilayer printed circuit boards, there is a quality management for carrying out laminated bodies by automatic optical inspection (ΑΟΙ), typically ranging from 450 nm to about 650 nm. Ultraviolet (UV) absorbance measurements were taken at the wavelengths, which may be measured via a υν-Vis meter. On the other hand, it is preferred that the phosphorus-modified flame retardant curing agent compound excellent in UV shielding performance is obtained by a slight excess of a phenolic compound and a phosphorus-modified phenolic compound and an aldehyde compound under an acid catalyst. 'Available as a novolak varnish reaction, and an excess of the phenolic compound and/or the phosphorus-modified phenolic compound can be removed by steaming. Further, 'the acid catalyst used for the novolac reaction of the present invention' can be removed by neutralizing and most of the water washing works using an aqueous solution of an alkali compound such as NaOH, KOH or NA2C〇3 in addition to oxalic acid which is separated by heat. The engineering of the residual acid catalyst is not limited to this method, and can be separated by various methods. According to a preferred embodiment of the present invention, the phosphorus-modified flame retardant curing agent produced by the novolak reaction may be any one of 21 201144414 compounds represented by the following Chemical Formulas 7 to 8.

〔化7〕 A A

m

In Chemical Formulas 7 and 8, the A series are each independently: OH

22 201144414

The Ri series are each independently:

R2 and R3 are each independently hydrazine, alcohol, alkoxy, ether, _, _, carboxy, hydroxy, thiol or cyano; or substituted or unsubstituted pharmaceutically, substituted or Substituted C! C10, a substituted or unsubstituted Cl~Ci〇 group, or a substituted or unsubstituted C1~C1G aromatic compound, substituted or #substituted C-C10 a substituted, unsubstituted or unsubstituted Cl~c heterocyclyl which may be any of an alcohol, an alkoxy group, a hydrazine, a vinegar, a hydrazine, a carbonyl group, a thiol group, a thiol group and a cyano group. X is each independently η; or a substituted or unsubstituted alkyl of Ci~Ch), which is an alcohol, an alkoxy group, an at, a ketone, a ketone, a thiol, a thiol, and a thiol. Any one of the cyano groups; the Y groups are each independently s or S 〇 2; or the substituted or non-peak C1 to C1 () silk, the substitution may be an alcohol, a hospitaloxy group, a hydrazine, a s And ketone, silk, mercapto, thiol and cyano are more than ten; t η are each independently an integer of 丨~2; and m are each independently an integer from 〇 to 1 such that Part a will be covalent Valence atoms. According to a preferred embodiment of the present invention, there is provided a resin composition comprising a phosphorus-modified flame retardant curing agent excellent in UV shielding properties of any one of the novelizing mouths represented by the chemical formulas 7 to 8. . The phosphorus-modified flame retardant S] agent which is excellent in the UV shielding property of the present invention produced by the method is considered to be % relative to the resin component lion when considering the improvement of the mechanical property and the improvement of the flame retardant property. Adding 50% by weight of the flame retardant curing agent, preferably adding 1G to 3G% by weight. In this case, it is an excellent flame retardant, heat-resistant property, physical and chemical substance imparted to the 1U chemical agent, and a raw material of the epoxy resin, the cyanate resin, the acrylic resin, and the epoxy resin can be used. . These high-reliability electrical and electronic insulation materials can be widely applied to the self-purifying PCB substrate listening edge (4), various composite materials, and adhesives, which require excellent flame retardancy and thermal stability. Coating agent, paint, etc. In particular, in the field of electronic applications such as high-density multilayer printed circuit boards, there is a quality management for implementing laminated bodies by automatic optical inspection (AOI). On the other hand, according to a preferred aspect of the present invention, the resin composition containing the flame retardant curing agent comprises an epoxy resin and a curing agent, an inorganic substance, a catalyst or the like which are usually used alone or in combination. Specifically, the epoxy resin to be added is not limited as long as it is contained in a resin composition used for a usual printed circuit board or the like, and is preferably selected from bisphenol A type epoxy resin and double. Phenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, indophenol varnish type epoxy resin, Dcpd type epoxy resin, double hope A Acid varnish type epoxy resin, bisphenol J7 with varnish type epoxy resin, a pair of varnish type epoxy resin, double § 盼 varnish type 24 201144414 epoxy resin, biphenyl novolac type epoxy resin, Any one or more of a xylenol varnish type epoxy resin, a DCPD phenol novolak type epoxy resin, a biphenyl stupid 2 novolak type epoxy resin, and a phenylphenol novolak type epoxy resin group. According to another preferred embodiment of the present invention, the curing agent constituting the resin composition may be used without limitation as long as it is contained in a resin composition used for a usual printed circuit board or the like, and may be selected from a phenol novolak type curing agent. A

Phenolic novolac type curing agent, bisphenol F novolac type curing agent, bisphenol AD secret varnish type curing agent, Shuangpan 8 secret varnish type curing agent, dimethyl stupid varnish type curing agent, DCPD phenol novolac type curing agent Any one or more of the stupid base phenolic varnish type m-forming agent, the stupid base (four) paint-type curing agent and the dicyandiamide group. According to another preferred embodiment of the present invention, the inorganic substance contained in the resin composition is used as long as it is contained in the tree residue of the ordinary printed circuit board or the like (4), and can be used without limitation. Any one of the stone groups. Etc. According to another preferred embodiment of the present invention, the catalyst constituting the resin composition is used without limitation as long as it is included in the composition of the substrate or the substrate. Specifically, it is used as a catalyst. 2_Methyl iodide, 2_ethyl·4_methyl^, 2_undecylcarbazole, 2-heptadecylimidazole, 2-phenylidene imidazole, 2-phenylene may be used singly or in combination. Ice methylimidazole dibromo 2·^°m嗤, 2·aminoethyl·2_mercapto-, 1·cyanoethyl-2-phenyl_4,5, di(cyano) The base oxymethyl) material, etc., but not limited to this. 25 201144414 According to another preferred embodiment of the present invention, the UV shielding efficiency of the resin composition may be 95% or more in the range of 100 to 400 nm in the UV field. The invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention. &lt;Production Example 1&gt; In a reaction tank, a polyformaldehyde 90.32 (1.25 mol), 30 g of water, and 3.3 g of an aqueous sodium hydroxide solution in a phenol 94.1 lg (l mole) were charged and heated while stirring. After the reaction was carried out at a temperature of 50 ° C for 5 hours, a neutralization reaction was carried out using 41.5 g of water and 1.67 g of sulfuric acid 0.1 N sulfuric acid, and then 255 g of decyl alcohol was added thereto, and then the reaction was carried out at a temperature of 70 ° C for 5 hours, and then charged. DOPO207.36g. Next, while removing methanol, the reaction was carried out at a temperature of i4 ° C for 10 hours or more to prepare a phosphorus-modified DOPO-phenol. Hereinafter, DOPO-bisphenol A and DPO_ are also produced by the method. &lt;Example 1&gt; Into a reaction tank, 564.66 g (6 mol) of phenol and 32. 1 g of D0P0-phenol (1 mol) were charged, and while DOPO-phenol was dissolved at a temperature of 9 ° C while heating and stirring, The acid catalyst oxalic acid 8.87 g was divided into three inputs to carry out the reaction. Next, Glyoxal (40% aqueous solution) i45 g (1 mol) was introduced in 5 portions to carry out the reaction. Subsequently, after reacting for 6 hours at a temperature of 卯*^, it was an oxalic acid which decomposed into an acid catalyst, and an additional reaction was carried out at 15 〇t. To remove unreacted phenol, at 200. (:, under vacuum, after phenol recovery, a phosphorus-modified flame retardant curing compound 517g with excellent UV shielding performance of 5.68% was obtained (FT-IR result: phenolic hydroxyl group (phen〇1_like 26 201144414) Hydroxyl group) : 3300cm'1' P = O : nOOcm'VnSOcm'1' PC-0 (aromatic): 9721-1, PC (aromatic) 14240^1) Evaluation of UV shielding properties of curing agent compounds In the case of using a UV-Vis measuring instrument, the results are shown in Fig. 1 below. <Example 2> 564.66 g (6 mol) of phenol and DOPO-phenol (p = 9.59%) 646.21 g were charged into the reaction vessel. (2 mol), while heating and stirring, dissolving D0P0-phenol at a temperature of 902⁄4, and then introducing the acid-catalyzed oxalic acid 12. "3 times. Next, glyoxal (40% aqueous solution) 145 g (1 mol) The reaction was carried out in 5 minutes, and then at a temperature of 90. (After the reaction for 6 hours, the oxalic acid decomposed into an acid catalyst was subjected to an additional reaction at 150 ° C to remove the unreacted phenol. After phenol recovery at 200 ° C under vacuum, a UV-shielding performance of 8.73% was obtained. Burning curing agent compound 646g (FT-IR result: expectation base: 3300cm·1, P=0: Ι200αη /1280cm 1, PC-Ο (aromatic): 972cm·1, PC (aromatic) 1424cm· 1) When the UV shielding property of the curing agent compound was evaluated, a UV_Vis measuring instrument was used, and the results are shown in Fig. 2 below. <Example 3> The age of the reactor was 564.66 g (6 m), DOPO- Double A (P = 9.4%) 680 g (l mole), while heating and stirring, while dissolving DOPO-bisphenol A at temperature 9 (rc, the acid-catalyzed oxalic acid 12 44 § was divided into three times. Next, Glycolaldehyde (40% aqueous solution) i45 g (1 mol) was charged in 5 times to carry out the reaction. Then, after 6 hours of reaction at a temperature of 9 ° C, the oxalic acid which is an acid catalyst was obtained as a fraction of 27 201144414. The reaction was further carried out at 150 ° C for 1 hour. In order to remove the unreacted phenol, a phosphorus-modified flame retardant having an excellent UV blocking property of 7.0% of phosphorus was obtained after phenol recovery in 2 Torr under vacuum. Curing agent compound 858g (FT-IR results: phenolic hydroxyl group: 3300 CHT1, P=〇: 12〇〇cm 1/1280crl, PC-0 (aromatic): 972cm·1, P, C ( Aromaticity) 1424CIT1) A UV-Vis measuring instrument was used to evaluate the UV shielding properties of the curing agent compound, and the results are shown in Fig. 3 below. &lt;Example 4&gt; Phenol 564-66 g (6 mol) and DPO-Phenol (P -10%) 31 〇g (丨mol) were charged into the reaction vessel while stirring at a temperature of 9 Torr. 〇 〇1&gt;〇_dissolved after the acid catalyst oxalic acid 8.74g was put into 3 times. Next, 145 g (1 mol) of Ethylene (40% aqueous solution) was introduced in 5 portions to carry out the reaction. Then 'at a temperature of 9 〇. (: After 6 to 7 hours of reaction, the oxalic acid decomposed into an acid catalyst was subjected to an additional reaction at 150 ° C for 1 hour. To remove unreacted phenol, a phenol recovery process was carried out at 200 C to obtain a phosphorus content of 5 71. % uv shielding performance of phosphorus-modified flame retardant curing agent compound 515g (FT-IR results: phenolic hydroxyl group: 3300cm·1, p=〇: 1200^/1280011 -1, pco (aromatic): 972αιΓΐ, p_c (aromatic) 1424 αιΓ1). The uv_vis measuring device is used for the masking property of the flat curing agent compound, and the results are shown in Fig. 4 below. <Example 5> Into the reaction tank 564 66g (6 moles), D〇p〇_ test (p = 28 201144414 9.59%) 323.11g (1 mole) and heated and stirred, while the DOPO-phenol is dissolved at a temperature of 9〇ac, the acid is The contact oxalic acid 12]^ was divided into 3 inputs. Then, 2 hours of p-Tefephthalaldehyde 5 〇% solution (Tolunen) 264 g (1 mol) was divided and the reaction was allowed to proceed. After 9 to 7 hours of reaction at 9 ° C, the oxalic acid decomposed into an acid catalyst was carried out at 15 ° C for 1 hour. In addition, in order to remove unreacted phenol, 568 g of a scale-modified flame retardant curing agent compound having excellent UV shielding performance with a phosphorus content of 4.9% was obtained after 2 〇〇〇c recovery (FT-IR results: Phenolic hydroxyl group: 3300 cm·1, P = 〇: mocuf VmOcm-1, PC-0 (aromatic): 972 cm-1, PC (aromatic) 1424 (^1). UV shielding property of pinger curing agent compound In the case of using a UV_Vis measuring device, the results are shown in Fig. 5 below. <Comparative Example 1> In addition to adding a triphenyl phosphate (phosphorus content: 9.5%, ei8〇4PH15) as a phosphorus compound, 326 g is substituted for DOPO-phenol. In the same manner as in Example 1, 655 g of a flame retardant curing agent compound having a phosphorus content of 4.36% was obtained. A UV-Vis measuring device was used for the UV shielding properties of the valence curing agent compound. Fig. 6 &lt;Comparative Example 2&gt; Methyl cellosolve (Methyl Cellosolve) and DOP 〇-(P = 9.59%) 323.11 g (1 mol) were added to the reaction vessel while heating and stirring. 90Ϊ dissolved DOPO-phenol. Then, after the acid catalyst oxalic acid 3.23g was divided into 3 inputs, glyoxal (4〇%) The solution was subjected to a reaction of 36.25 g for 2 hours, and the reaction was allowed to proceed. Then, after the reaction was carried out at a temperature of 90 ° C for 10 29 201144414 hours, the ketone-based cellosolve was removed at 150 ° C for the decomposition of the oxalic acid to the acid catalyst. After the addition of the methyl cellosolve for 1 hour, the amount of the modified flame-retardant curing agent compound having a UV content of 9.1% was obtained (FT-IR result: phenolic hydroxyl group: 3300011], P = 0: 1200 cin / 1280 cm, PC-0 (aromatic): 972 CIH · 1, PC (aromatic) 1424 cm · 1). A UV-Vis measuring instrument was used to evaluate the UV shielding properties of the curing agent compound, and the results are shown in Fig. 7 below. On the other hand, in Fig. 8, a phenol phenol aldehyde varnish curing agent (phen〇i NoVolac Hardener) having a 〇H EEW103g/OH, a solid content of 55%, and a softening point of 110 ° C is used. The measurement results. &lt;Evaluation Example&gt; A flame-retardant curing agent compound produced by the above-described Examples 丨 to 5 and Comparative Examples 丨 to 2 was blended as in the following Tables 2 to 4 to produce a printed circuit. An adhesive for the substrate. Further, in order to evaluate the physical properties of the tank-modified flame retardant curing agent compound produced in the examples and the comparative examples, blending as shown in Tables 2 to 4 was carried out, and the results were shown. Specifically, the varnish produced by blending the lysates of the examples and the comparative examples with the blending ratios shown in the following Tables 2 to 4 was used to prepare a varnish, and then impregnated with glass fibers to carry out a prepreg operation. Prepreg is tied to 175. (: After making 5 minutes of semi-hardening (4), 8 weights will be pressurized for 1 minute under a pressure of 1 thief and 25kgf/em2, then '12 hours of additional pressure for 4 〇kgfW. Then 'freeze in the refrigerant. 30 minutes. 201144414 (1) The flame retardancy test is carried out according to the UL-94 method. Specifically, the test piece is "5xl/2"' using 5 test pieces and the test piece is exposed to cremation for 10 seconds, then the spark is removed. The test piece is extinguished, and after 10 seconds of contact, the method of removing the spark is again performed, and the sum of the five test #丨, 2: the underburning time is calculated (the sum of the 1-two burning times is less than 50 seconds, the flame retardant level) For the case of V-0 '50 seconds or more to 250 seconds or less, it is V-1). (2) Measurement of glass transition temperature The experiment uses a differential thermal analyzer (DSC) (20/min). (3) Peel strength ( Peel Strength was determined according to the method of GISC-6471. (4) Evaluation of UV shielding was performed using SINC0 s_31〇〇 equipment to determine 〇(5) Gelation time was determined at 170 ° C using a gel timer. (6) The UV shielding ratio is determined by using the UV-Vis measuring device as shown in Tables 2 to 4, at 1〇〇. 4〇〇n[n, the average value of the uv masking rate is shown in Table 1. [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% 31 201144414 [Table 2] Resin Composition 1 (Example 1) Tree 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 Phosphorus modified epoxy resin 0 0 0 KDT-4400 0 0 0 Flame retardant curing agent (Example 1 to Comparative Example 2) (NY60%) 131.3 87.26 114.5 Phenolic novolac curing agent 0 53.54 41.63 Dicy 2 2 2 Meteorite 44.69 45.45 47.9 MCs 44.69 45.45 47.9 2MI 0.01 0.01 0.01 Composition UV shading OK OK OK Flame retardant grade / burning time V-0 (25s) V-0 (23s) V-0 (24s) Lin content 2.0% 2.0 % 2.0% Peel strength 1.4 1.3 1.4 170 Gelation time 199s 165s 175s Glass transition temperature 155.4 166.82 173.2 32 201144414 [Table 3] Shuyue Duocheng 4 (Example 4) Resin composition 5 (Example 5) Composition 1 (Financial Example 1) Crossing Composition 2 (Comparative Example 2) YD-011M68 14.7 14.7 14.7 14.7 YDPN-638A 80 112.5 112 .5 112.5 112.5 Phosphorus modified epoxy resin 0 0 0 0 KDT-4400 0 0 0 0 Flame retardant curing agent (Example 1 to Comparative Example 2) (NV55%) 131.3 189 141.34 81.33 Phenolic novolac curing agent 0 0 0 56.72 Dicy 2 2 2 2 Meteorite 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 shading OK OK OK OK Flame retardant grade / burning time V-0 (21s) V-0 (45s) Vl ( 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 gelation time 205s 195s 210s 170s Glass transition temperature 157.0 155.0 148.6 150.5 33 201144414 [Table 4] Resin composition 3 (implementation Example 3) Comparing resin composition

YD-011M68 YDPN-638A80 Phosphorus modified epoxy resin KDT-4400 Flame retardant curing agent (Example 1 to Comparative Example 2) (NV60%) Phenolic novolac curing agent

Dicy Diamond MCs

2MI composition UV shielding flame retardant phosphorus content peeling strength 170 gelation time glass transition temperature FIG. 1 to FIG. 8 show the phosphorus-modified flame retardant curing agent and the UV shielding performance of the comparative example produced according to the present invention. , the χ axis indicates the light, the skin length is wavelenth), and the y axis indicates the light transmittance. The light shielding effect of this wavelength band from the second to the eighth light. In the wavelength band, it is known that the closer to 1_the more the shielding effect is, the closer to (4) the shielding effect is excellent at the wavelength, but according to the present invention, the phosphorus which is produced and has excellent shielding performance is known. The UV transmittance of the modified curing agent in the KUV field at 1〇-39〇nm. 34 201144414 ΜCuring ^ Figure 1 to Figure 8 and Table 1 show that the reduction of the UV valence of the curing agent in the first to fifth embodiments of the present invention is superior to that of the comparative example Κ 2 (4) and According to Tables 2 to 3, it is known that the flame retardant curing agent composition of Examples 1 to 5 contains a Uv shielding effect and a reactive flame retardant: compared to the comparative resin composition of the Timing agent, there is a so-called It is excellent in strength and has a high glass transition temperature and excellent flame retardancy. According to the table, it is known that, in the case of the resin of the present invention, the phosphorus of the flame retardant property of the noodles resin itself has a υν shielding property, and no other epoxy resin is added in the manufacture of the machine composition. It is an epoxy resin and an epoxy resin (KDT.44G0, Guodu Chemical Co., Ltd.) having UV shielding properties, and its performance is exhibited. Specifically, from the results of Table 4, it is understood that the glass transition and the adhesion are remarkably reduced in the case where a flame-retardant epoxy resin is added. Gas [Industrial Applicability] The UV-shielding property produced by the production method of the present invention is excellent, and the modified MSI agent and the resin composition containing the same can be widely applied to a PCB substrate and insulation. A variety of composite materials, coatings, coating agents, and coatings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the UV shielding rate of a flame retardant curing agent produced by a preferred embodiment of the present invention. Fig. 2 is a graph showing the UV shielding rate of a flame retardant curing agent produced by a preferred embodiment of the present invention. 35 201144414 Figure 3 is a graph showing the UV shielding rate of a flame retardant curing agent produced by a preferred embodiment of the present invention. Figure 4 is a graph showing the UV shielding rate of a flame retardant curing agent produced by a preferred embodiment of the present invention. Fig. 5 is a graph showing the UV shielding rate of a flame retardant curing agent produced by a preferred embodiment of the present invention. Fig. 6 is a graph showing the UV shielding rate of the flame retardant curing agent produced by Comparative Example 1. Fig. 7 is a graph showing the UV shielding rate of the flame retardant curing agent produced by Comparative Example 2. Fig. 8 is a UV shielding rate diagram of OH.E.E.W103g/eq, a solid component of 55%, and a softening point of 10 °C, Phenol NoVolac Hardener. [Main component symbol description] None. 36

Claims (1)

201144414 VII. Patent application scope: 1 · A method for producing a phosphorus-modified flame retardant curing agent excellent in uv shielding performance, characterized in that it comprises: a phenolic compound (1) and a chemical formula 丨~2 represented by the following a step of producing a flame-retardant curing V agent by reacting a phosphorus-modified phenol compound (2) of any one or more of the compounds with a phenolic varnish in the presence of an acid catalyst, [Chemical Formula 1] 〔化2〕 In the chemical formulas 1 to 2, the cardiac systems are each independently: 37 201144414 R: 酉, 酉, carboxy, hydroxy, thiol or cyano; or substituted or unsubstituted C~r 甘, C, ~c10, it, 1 Cl ° alkyl, substituted Or not taken ~ 席 席 、, substituted or - replaced by C1 ~ C 1 (hybrid, the substitution can be: base:: generation or non-taken - alcohol, alkoxy, ether one -r-i, a acetylene group which is substituted or unsubstituted by a -J substituted or unsubstituted Cl~Cl°, and f substituted by a scaly peak Q~^ shirt, a non-substituted Cl~C-like material. Any of the non-Hanni or ether, ester, ketone, carboxyl, sulfhydryl, thiol and cyano groups, which are each independently substituted or substituted or unsubstituted, Ci~Ciq, The substitution may be any one of an alcohol, a meta-soil, a sulphur, a sulphur, a thiol, a thiol, a thiol, and a cyano group, and each of them is independently S or so2; or = substituted or not Substituting the filaments of C1 to C1G, the substitution may be any one of an alcohol, a terpolymer, a vinegar, a _, a thiol, a thiol, a thiol, and a cyano group; the n series are each independently 1 to 2 Integer. For example, the scale of the i-th patent application scope Quality of the flame retardant curing agent manufacturing method, wherein the divergent ⑴ based compound represented by the following Chemical Formula 3 to 4 in the compound according to any one of the above: [Formula 3] 38 201 144 414 〔化4〕 In the chemical formulae 3 to 4, each of the X groups is independently hydrazine; or a substituted or unsubstituted alkyl group of Ci-Cio, and the substitution may be an alcohol, an alkoxy group, an ether, a vinegar, a ketone, a ketone group, or a ketone group. Any one of a radical, a thiol or a cyano group; the Y series are each independently S or S〇2; or a substituted or unsubstituted C-C1G alkyl group, the substitution may be an alcohol or an alkoxy group Any one of ether, vinegar, ketone, thiol, thiol, thiol and cyano. 3. The method for producing a phosphorus-modified flame retardant curing agent according to claim 2, wherein the phenolic compound (1) is selected from the group consisting of phenol, indophenol, phenol, butyl, octyl expectation, Any one of a group consisting of phenyl, sulphur, oxy, ethoxylated, bisphenol A, bisphenol F, bisphenol S, and bisphenol AD. 39 201144414 4' The method for producing a modified flame retardant curing agent according to the fourth aspect of the invention, wherein the compound (1) and the phosphorus-modified lanthanide compound represented by the chemical formulas 1 to 2 (2) And the molar ratio of 4 5 . 1 to 20 : 1 is reacted with respect to the disc compound. For example, the manufacturer of the phosphorus-modified flame retardant curing agent according to the third paragraph of the patent scope is selected, wherein the acid catalyst is selected from the group consisting of oxalic acid, P-benzenesulfonic acid, sulfonic acid, salt 酉久水/奋液, Any one or more of the group of 6 consisting of a sulfuric acid aqueous solution, a nitric acid aqueous solution, and a phosphoric acid aqueous solution. For example, the manufacturer of the modified flame retardant curing agent of the fourth aspect of the patent application is a compound in which any of the compounds represented by the following chemical formulas 5 to 6 is: [Chemical 5] Ο 〇 [6] X is each independently H; or a substituted or unsubstituted alkyl of Q to Ciq, which may be an alcohol, an alkoxy group, a ruthenium, a ketone, a decyl group, a hydroxy group, a thiol, and a cyano group. Any one or more. A method for producing a phosphorus-modified flame retardant curing agent according to the first aspect of the invention, wherein the phosphorus-modified flame retardant curing agent 201144414 produced by the production method is a compound represented by the following chemical formulas 7 to 8. Any one or more: [Chemical 7] AA In Chemical Formulas 7 and 8, the A series are each independently: OH At least one of the A is: 41 201144414 OH The Ri series are each independently: R 2 and R 3 are each independently Η, carboxyl, hydroxy, thiol or cyano; alcohol, alkoxy, ether, or Substituting the cl generation: Substituting the base of the &amp;~Cl°, substituted or non-substituted A. a substituted, unsubstituted or substituted or substituted substituted aromatic compound of Cl~Ci〇, a non-substituted Cl~C^ thiol group, a peak or a non-substituted c-generation or Miscellaneous, heterogeneous, silk, m 1 i. Any of the above, thiol and cyano groups; soil, hydroxy X are each independently H; or substituted or hetero-substituted Ci~Cig age, substituted alkoxy, m-filament, μ-based, In the thiol and cyano group, J, or more; 1 to Υ are each independently S or s〇2; or substituted or unsubstituted alkyl of Ci~Ciq, which is taken as alcohol 42 201144414 alkoxy Any one or more of an ether, an ester, a ketone, a carboxyl group, a hydroxyl group, a thiol, and a cyano group; the η series are each independently an integer of 1 to 2; and the m systems are each independently an integer of 0 to 1, such that The valence of the carbon atom that satisfies the covalently bound portion of the oxime. 8. The method for producing a phosphorus-modified flame retardant curing agent according to claim 1, wherein the phosphorus-modified flame retardant curing agent having excellent UV shielding properties has a phosphorus content of from 1 to 15%. 9. A resin composition comprising: a phosphorus-modified flame retardant curing agent having excellent U V shielding properties of any one of the compounds represented by the following Chemical Formulas 7 to 8: [Chem. 7] 〔化8〕 In Chemical Formulas 7 and 8, the A series are each independently: 43 201144414 X- ICfH or Rll, xv At least one of the A is: The Ri series are each independently: R2 and I are each independently H, an alcohol, an alkoxy group, an ether, an ester, a carboxyl group, a hydroxyl group, a thiol or a cyano group; or a red substituted or non-fluorene-substituted Ci~CiQ filament, substituted or non-sea Instead of the alkenyl, substituted or unsubstituted &amp;~Cl of Ci~c1G. a substituted or unsubstituted C丨~C〗 aromatic compound, substituted C, ~c1G, substituted, substituted, c~c: alkyl, the substitution Is an alcohol, an alkoxy group, an ether, a ketone, a carboxy group, a hydroxy group, a thiol or a cyano group; the X series are each independently Η; or a substituted or unsubstituted Ci a Cig group which is an alcohol, an alkoxy group, an ether, an ester, a ketone, a carboxyl group, a hydroxyl group, a thiol or a cyano group; the y series are each independently s or so2; or substituted Or an unsubstituted CcCw alkyl group, the substitution may be 'any of an alcohol, an alkoxy group, an ether, an ester, a ketone, a carboxyl group, a hydroxyl group, a thiol and a cyano group; the η series are each independently 丨~ An integer of 2; and m are each independently an integer from 〇 to 丨, such that the valence of the carbon atom satisfying the covalently bonded portion of the oxime portion is satisfied. 10. The resin composition of claim 9 wherein the flame retardant curing agent is 10 to 50% by weight based on 100% by weight of the total resin composition. 11. The resin composition of claim 9, wherein the resin composition has a UV shielding efficiency of 95% or more in the uv field of 1 〇〇 to 4 〇〇ηη. A resin composition for a printed circuit board, which comprises the resin composition according to any one of claims 9 to 11. A printed circuit board comprising a resin composition for a printed circuit board according to the first aspect of the application. 45