WO2022239955A1 - Composition d'agent durcissant ignifuge pour époxy, et agent durcissant ignifuge pour époxy la comprenant - Google Patents
Composition d'agent durcissant ignifuge pour époxy, et agent durcissant ignifuge pour époxy la comprenant Download PDFInfo
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- WO2022239955A1 WO2022239955A1 PCT/KR2022/004079 KR2022004079W WO2022239955A1 WO 2022239955 A1 WO2022239955 A1 WO 2022239955A1 KR 2022004079 W KR2022004079 W KR 2022004079W WO 2022239955 A1 WO2022239955 A1 WO 2022239955A1
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- independently
- epoxy
- curing agent
- compound represented
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the present invention has a high glass transition temperature, low hygroscopicity, excellent adhesion, high peel strength, low thermal expansion coefficient, significantly improved electrical properties such as dielectric constant and dielectric loss, as well as flame retardancy, which will be widely used in the electric and electronic fields. It relates to a flame retardant curing agent for epoxy that can be used.
- epoxy resin with excellent electrical properties, mechanical properties, adhesiveness, etc. is widely used, and as a curing agent, active materials such as amine compounds and phenol compounds Curing agents containing hydrogen are widely used.
- Korean Patent No. 1203150 discloses an epoxy resin composition that can be usefully used as an adhesive and sealing material for electronic devices, but in the case of a curing agent included in the composition, a conventional amine-based curing agent is used, thereby reducing the dielectric constant and dielectric loss of the cured product. It cannot be minimized, the hygroscopicity of the cured product is high, and the adhesive strength cannot be increased, so that it cannot be used as a high-performance, highly integrated electrical and electronic material.
- an organic halogen compound when imparting flame retardancy to an epoxy resin, an organic halogen compound has been used as a flame retardant.
- flame retardancy is excellent, but there is a problem in that dioxins, which are classified as toxic gases, are generated during molding or incineration. Therefore, the use of phosphorus-based flame retardants has been proposed as flame retardants replacing organic halogen compounds.
- Korean Patent Registration No. 10-1462309 discloses an amino group-containing phosphoric acid ester flame retardant, but since it is an addition-type flame retardant, it does not act as a curing agent for curing by directly reacting with an epoxy resin, etc. When mixed with epoxy resin, it has the disadvantage of lowering the physical properties of epoxy, so improvement is needed.
- the present invention has been made to solve the above problems, the problem to be solved by the present invention is to directly impart flame retardancy to a curing agent, and the cured product to which the curing agent is applied has excellent flame retardancy, high glass transition temperature, low moisture absorption, and excellent adhesive strength.
- a flame retardant curing agent for epoxy having high peel strength and low coefficient of thermal expansion and at the same time significantly improving electrical properties such as dielectric constant and dielectric loss.
- the second problem to be solved by the present invention is that the curing agent of the present invention has flame retardancy, high glass transition temperature, low moisture absorption, excellent adhesion, high peel strength, and low thermal expansion coefficient, while having remarkable electrical properties such as dielectric constant and dielectric loss.
- an electrical/electronic encapsulant or a laminate for electrical/electronic substrates is provided.
- the flame retardant curing agent for epoxy of the present invention may include a compound represented by Formula 1 having a weight average molecular weight (Mw) of 1,000 to 10,000.
- a 1 and A 2 are each independently hydrogen or And, at least one of A 1 and A 2 is not hydrogen,
- Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q 7 , Q 8 , Q 9 , Q 10 , Q 11 and Q 12 are each independently hydrogen or 2 carbon atoms having at least one double bond
- a straight-chain alkyl group of ⁇ 5, Z 1 , Z 2 and Z 3 are each independently or , E 1 , E 2 , E 3 , E 4 , E 5 and E 6 are each independently , or , X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 are each independently , Or a straight-chain alkylene group having 1 to 5 carbon atoms, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are each independently a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms, a, b, d and e are each independently a rational number ranging from 0 to 8,
- the compound represented by Formula 1 may be a compound represented by Formula 2 below.
- a 3 and A 4 are each independently hydrogen or And, at least one of A 3 and A 4 is not hydrogen,
- Q 13 , Q 14 , Q 15 , Q 16 , Q 17 , Q 18 , Q 19 , Q 20 , Q 21 , Q 22 , Q 23 and Q 24 are each independently hydrogen or 2 carbon atoms having at least one double bond ⁇ 5 linear alkylene group
- Z 4 , Z 5 and Z 6 are each independently or
- E 7 , E 8 , E 9 , E 10 , E 11 and E 12 are each independently , or , X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 and X 16 are each independently , Or or a straight-chain alkylene group having 1 to 5 carbon atoms
- R 7 , R 8 , R 9 , R 10 , R 11 , R 12 are each independently a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms
- l, m , p, q are each independently a rational number ranging from 0 to 8,
- the curing agent is a compound represented by Formula 3; a compound represented by Formula 4; And an endcapping agent represented by Formula 5; may include a copolymer obtained by copolymerizing a mixture including a.
- X 17 and X 18 are each independently , or a straight-chain alkyl group having 1 to 5 carbon atoms and having at least one double bond, and n is a rational number of 0 to 8.
- E is , or and M 1 and M 2 are each independently F, Cl, Br or I.
- G 1 , G 2 , G 3 , and G 4 are each independently hydrogen or a straight-chain alkyl group having 2 to 5 carbon atoms and having at least one double bond, and Z is or And, R 13 and R 14 are each independently a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms.
- the copolymer is a compound represented by the formula (4); And a compound represented by Formula 3; may be included in a molar ratio of 1: 0.1 to 1.7, and the molar ratio of the compound represented by Formula 3 may be based on the number of moles of phenolic hydroxyl groups (OH groups).
- the flame retardant curing agent composition for epoxy is a compound represented by the formula (3); a compound represented by Formula 4; And a terminal blocking agent represented by Formula 5; may include.
- the flame retardant curing agent for the epoxy It is possible to manufacture an electrical/electronic encapsulant comprising a; and an epoxy resin.
- the flame retardant curing agent for the epoxy As another object of the present invention, the flame retardant curing agent for the epoxy; And an epoxy resin; it is possible to manufacture a laminate for electrical and electronic substrates containing a.
- the flame retardant curing agent for the epoxy As another object of the present invention, the flame retardant curing agent for the epoxy; And an epoxy resin; it is possible to prepare a flame retardant epoxy resin composition, including.
- the flame retardant curing agent for epoxy of the present invention exhibits excellent thermal stability due to the high glass transition temperature of the cured product, and has low moisture absorption to minimize moisture absorption in semiconductors, etc., thereby preventing internal separation or cracking of semiconductors in the soldering process. have.
- the durability of the cured product is remarkably increased, and at the same time, it is possible to prevent curvature of packaging by having a low coefficient of thermal expansion.
- dielectric constant, dielectric loss, etc. are significantly improved, enabling high-density integration of semiconductors according to remarkable improvement in electrical insulation properties, and thus can be widely used in electrical and electronic encapsulants and laminates.
- FIG. 1 is a graph showing the analysis of a flame retardant curing agent for epoxy according to an embodiment of the present invention through gel permeation chromatography (GPC, SHIMADZU);
- Figure 2 is a graph showing the analysis of the flame retardant curing agent for epoxy according to an embodiment of the present invention through infrared spectroscopy (IR).
- IR infrared spectroscopy
- curing agents having active hydrogens such as amine compounds and phenol compounds are conventionally used as curing agents for epoxy resins, but curing agents having active hydrogens as described above curing epoxy resins
- curing agents having active hydrogens as described above curing epoxy resins
- the hygroscopicity of the final cured product is increased, and electrical properties such as dielectric constant (Dk) and dielectric loss (Df) are deteriorated.
- the present invention sought to solve the above problems by providing a flame retardant curing agent for epoxy comprising a compound represented by Formula 1 below.
- a 1 and A 2 are each independently hydrogen or (hereinafter, referred to as formula (1a)).
- each A 1 and A 2 are each independent, but also each A 1 and/or each A 2 is independent.
- each A 1 and/or each A 2 is independent.
- Formula 1 when a is 3 and b is 2, there are 3 A 1s and 2 A 2s included, and in this case, each A 1 is independent of each other, and each A 2 is independent of each other .
- At least one of A 1 and A 2 is not hydrogen. If A 1 and A 2 are both hydrogen, when the curing agent is cured with an epoxy resin, highly polar hydroxy is generated according to the reaction with the active hydrogen, so the hygroscopicity of the final cured product increases, and the dielectric constant (D k ), dielectric loss (D f ), etc., there may be a problem in that electrical characteristics are deteriorated.
- a and b are each independently a free number of 0 to 8, and more preferably, in terms of the glass transition temperature, heat resistance, and electrical properties of the cured product, a and b are each independently a free number of 1 to 8. can If a and / or b exceeds 8, there is a problem that is not suitable for use as a laminating material and an encapsulant because the surface of the cured material becomes uneven during curing with epoxy, resulting in problems with adhesive strength.
- c is a rational number of 0.1 to 10. If c is less than 0.1, there is a problem in that the heat resistance of the cured product is lowered and the glass transition temperature is lowered during curing with the epoxy, and it is difficult to implement the desired physical properties, such as lowering the electrical properties of dielectric constant and dielectric loss factor. In addition, if c exceeds 10, gelation may be formed, and when cured with epoxy, the surface of the cured product becomes uneven, resulting in problems with adhesive strength, which is a problem that is not suitable for use as a laminate or encapsulant. There may be.
- a 1 and A 2 are each independently hydrogen or in this case, in Formula (1a), A 1 and A 2 are each independent, and each A 1 and/or each A 2 is also independent.
- a 1 and A 2 are each independent, and each A 1 and/or each A 2 is also independent.
- d is 3 and e is 2
- each A 1 is independent of each other, and each A 2 is independent of each other .
- At least one of A 1 and A 2 is not hydrogen.
- the Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q 7 , Q 8 , Q 9 , Q 10 , Q 11 and Q 12 are each independently hydrogen or a straight line having 2 to 5 carbon atoms. It may be a chain alkylene group, preferably each independently hydrogen or a straight chain alkylene group having 2 to 4 carbon atoms, more preferably Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q 7 , Q 8 , Q 9 , Q 10 , Q 11 and Q 12 are each independently hydrogen, or can be
- the "straight-chain alkylene group" means one having at least one double bond in a straight-chain structure.
- d and e are each independently a rational number of 0 to 8, and more preferably d and e are each independently a rational number of 1 to 8 in terms of the glass transition temperature, heat resistance, and electrical properties of the cured product. If d and / or e exceeds 8, the surface of the cured material becomes uneven during curing with epoxy, resulting in problems with adhesive strength, which may cause problems that are not suitable for use as laminates and encapsulants.
- f is a rational number of 0 to 8
- f is a rational number of 1 to 8 in consideration of heat resistance, glass transition temperature, and electrical properties of the cured product. If f exceeds 8, gelation may be formed, and when cured with epoxy, the surface of the cured material becomes uneven, resulting in problems with adhesive strength, so there may be problems that are not suitable for use as laminates and encapsulants. have.
- Z 1 , Z 2 and Z 3 are each independently or And, E 1 , E 2 , E 3 , E 4 , E 5 and E 6 are each independently , or can be
- X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 are each independently , Or a straight-chain alkylene group having 1 to 5 carbon atoms, preferably each independently , Or it may be a straight-chain alkylene group having 1 to 3 carbon atoms.
- R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 may each independently be a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, preferably R 1 , R 2 , R 3 , R 4 , R 5 , R 6 may each independently be a hydrogen atom or a linear alkyl group having 1 to 2 carbon atoms, more preferably R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 may each independently be a methyl group.
- the compound represented by Formula 1 may have a weight average molecular weight (Mw) of 1,000 to 10,000, preferably 1,500 to 5,000. If the weight average molecular weight is less than 1,000, there is a problem in that the heat resistance of the cured product is low and the glass transition temperature is low during curing with epoxy, and the electrical properties of dielectric constant and dielectric loss factor may also deteriorate. There is a possibility of formation, and when cured with epoxy, the peel strength of the cured product decreases, and the surface of the cured product becomes uneven, causing problems in adhesive strength, so problems that are not suitable for use as laminates and encapsulants may occur. Therefore, simply because the compound represented by Formula 1 does not express the desired physical properties of the present invention, it is not possible to express the desired physical properties of the present invention only when it has a structure represented by Formula 1 and satisfies a specific molecular weight range. can
- the compound represented by Formula 1 may be a compound represented by Formula 2 below.
- a 3 and A 4 are each independently hydrogen or (hereinafter, referred to as formula (2a)).
- each A 3 and A 4 are each independent, but also each A 3 and/or each A 4 is independent.
- each A 3 and/or each A 4 is independent.
- Formula 2 when p is 3 and q is 2, there are 3 A 3s and 2 A 4s included, and in this case, each A 3 is independent of each other, and each A 4 is independent of each other .
- At least one of A 3 and A 4 is not hydrogen. If the A 3 and A 4 are both hydrogen, when the curing agent is cured with an epoxy resin, highly polar hydroxy is generated according to the reaction with the active hydrogen, so the hygroscopicity of the final cured product increases, and the dielectric constant (Dk) , dielectric loss (Df) and other electrical characteristics may be degraded.
- l and m are each independently a free number of 0 to 8, and more preferably, in terms of the glass transition temperature, heat resistance, and electrical properties of the cured product, l and m are each independently a free number of 1 to 8. can If l and / or m exceeds 8, there is a problem that is not suitable for use as a laminate and encapsulant because the surface of the cured product becomes uneven during curing with epoxy, resulting in problems in adhesive strength.
- n is a rational number of 0.1 to 10. If n is less than 0.1, there is a problem in that the heat resistance of the cured product is lowered and the glass transition temperature is lowered during curing with the epoxy, and it is difficult to implement the desired physical properties, such as lowering of dielectric constant and dielectric loss factor. In addition, if n exceeds 10, gelation may be formed, and when cured with epoxy, the surface of the cured product becomes uneven, resulting in problems with adhesive strength, which is a problem that is not suitable for use as a laminate or encapsulant. There may be.
- r is a rational number of 0 to 8, and more preferably r is a rational number of 1 to 8 in consideration of heat resistance, glass transition temperature, and electrical properties of the cured product. If r exceeds 8, gelation may be formed, and when cured with epoxy, the surface of the cured material becomes uneven, resulting in problems with adhesive strength, so there may be problems that are not suitable for use as laminates and encapsulants. have.
- Z 4 , Z 5 and Z 6 are each independently or And, E 7 , E 8 , E 9 , E 10 , E 11 and E 12 are each independently , or can be
- X 9 , X 10 , X 11 , X 12 , X 13 , X 14 , X 15 and X 16 are each independently , Or a straight-chain alkylene group having 1 to 5 carbon atoms, preferably each independently , or a straight-chain alkylene group having 1 to 3 carbon atoms.
- R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each independently a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, preferably R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are each independently a hydrogen atom or a straight-chain alkyl group having 1 to 2 carbon atoms.
- Q 13 , Q 14 , Q 15 , Q 16 , Q 17 , Q 18 , Q 19 , Q 20 , Q 21 , Q 22 , Q 23 and Q 24 are each It may independently be hydrogen or a straight-chain alkylene group having 2 to 5 carbon atoms, preferably each independently hydrogen or a straight-chain alkylene group having 2 to 4 carbon atoms, more preferably Q 13 , Q 14 , Q 15 , Q 16 , Q 17 , Q 18 , Q 19 , Q 20 , Q 21 , Q 22 , Q 23 and Q 24 are each independently hydrogen, or can be
- straight-chain alkylene group means one containing at least one double bond in a straight-chain structure.
- the compound represented by Formula 2 may have a weight average molecular weight (Mw) of 1,000 to 10,000, preferably 1,500 to 5,000. If the weight average molecular weight is less than 1,000, there is a problem in that the heat resistance of the cured product is low and the glass transition temperature is low during curing with epoxy, and the electrical properties of dielectric constant and dielectric loss factor may also deteriorate. There is a possibility of formation, and when cured with epoxy, the peel strength of the cured product decreases, and the surface of the cured product becomes uneven, causing problems in adhesive strength, so problems that are not suitable for use as laminates and encapsulants may occur. Therefore, simply because the compound represented by Formula 1 does not express the desired physical properties of the present invention, it is not possible to express the desired physical properties of the present invention only when it has a structure represented by Formula 1 and satisfies a specific molecular weight range. can
- the flame retardant curing agent for epoxy according to the present invention is a compound represented by Formula 3; a compound represented by Formula 4; And a terminal capping agent represented by Formula 5; may include a copolymer obtained by mixing the flame retardant curing agent composition for epoxy including, and copolymerizing the mixture obtained by mixing.
- X 17 and X 18 are each independently , or a straight-chain alkylene group having 1 to 5 carbon atoms, and n is a rational number of 0 to 8.
- E is , or , and M 1 and M 2 may each independently be F, Cl, Br or I, and preferably, M 1 and M 2 may be Cl.
- Z is or And R 13 and R 14 are each independently a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms.
- X 17 and X 18 are each independently , Or it may be a straight-chain alkylene group having 1 to 5 carbon atoms, preferably X 17 and X 18 are each independently , Or it may be a straight-chain alkylene group having 1 to 3 carbon atoms.
- n may be a rational number of 0 to 8, preferably n may be a rational number of 1 to 8.
- R 13 and R 14 in Formula 5 may each independently be a hydrogen atom or a straight-chain alkyl group having 1 to 3 carbon atoms, preferably each independently a hydrogen atom or a straight-chain alkyl group having 1 to 2 carbon atoms. .
- G 1 , G 2 , G 3 and G 4 may each independently be hydrogen or a linear alkylene group having 2 to 5 carbon atoms.
- G 1 , G 2 , G 3 and G 4 may each independently be a straight-chain alkylene group having 2 to 4 carbon atoms, more preferably, G 1 , G 2 , G 3 and G 4 are each independently hydrogen, or can be
- the "straight-chain alkylene group” means one having at least one double bond in a straight-chain structure.
- the compound represented by Formula 4 and the compound represented by Formula 3 may be included in the mixture in a molar ratio of 1:0.1 to 1.7, preferably 1:0.5 to 1.5.
- the molar ratio of the compound represented by Chemical Formula 3 may be based on the number of moles of phenolic hydroxyl groups (OH).
- the compound represented by Formula 3 is included in an amount exceeding 1.7 molar ratio, gelation may be formed, and when cured with epoxy, the peel strength of the cured product decreases, and the surface of the cured product becomes uneven, resulting in problems with adhesive strength.
- the curing agent may have a low glass transition temperature and poor electrical properties such as dielectric constant and dielectric loss factor.
- the compound represented by Formula 4 and the endcapping agent represented by Formula 5 may be included in the mixture at a molar ratio of 1:0.1 to 1.7, preferably at a molar ratio of 1:0.5 to 1.5. have. If the endcapping agent represented by Formula 5 is included in a molar ratio of less than 0.1, flame retardancy may be deteriorated, and if the molar ratio is greater than 1.7, heat resistance may be deteriorated and glass transition temperature may be low.
- the compound represented by Formula 4 and the compound represented by Formula 3 were added at a molar ratio of 1:0.1 to 1.7, and the compound represented by Formula 4 and the endcapping agent represented by Formula 5 were added at a molar ratio of 1:0.1
- a mixture was prepared by adding and mixing at a molar ratio of ⁇ 1.7.
- the molar ratio of the compound represented by Chemical Formula 3 may be based on the number of moles of phenolic hydroxyl groups (OH).
- 200 to 600 parts by weight of an organic solvent may be included based on 100 parts by weight of the total mixture, and preferably 250 to 550 parts by weight of an organic solvent may be included. It is put into a reaction vessel equipped with a nitrogen inlet pipe, a thermometer, and a reflux condenser.
- the organic solvent may be used without limitation as long as it can be used in the preparation of a conventional curing agent for epoxy, and as a non-limiting example thereof, organic solvents such as toluene, methyl ethyl ketone, methyl isobutyl ketone, alone or Two or more types may be used in combination.
- the catalyst and acid catalyst may use a catalyst and an acid scavenger that can be used in a copolymerization step of a conventional curing agent, and non-limiting examples of the catalyst and acid scavenger include triethylamine, trimethylamine, and tripropylamine.
- pyridine, N-methyl piperidine and the like can be used alone or in combination of two or more.
- the salt produced by the copolymer and the adduct is precipitated.
- a desalting process may be performed by introducing a solvent such as water.
- the desalting process may be performed by vacuum degassing at 150 to 200 ° C. after dissolving the salt generated by the addition reaction and then proceeding with a liquid separation process to separate the copolymerized compound.
- the copolymer may have a weight average molecular weight (Mw) of 1,000 to 10,000, preferably 1,500 to 5,000, and the curing agent containing the copolymer satisfying the above range has a high glass transition temperature and excellent heat resistance.
- Mw weight average molecular weight
- Mechanical properties such as peel strength and moisture absorption resistance are expressed, and electrical properties can be improved by having a low dielectric constant and dielectric loss value, and flame retardancy can be imparted without impairing the physical properties of the epoxy resin.
- the cured product containing the epoxy resin and the flame retardant curing agent for epoxy according to the present invention can be used as an electrical/electronic encapsulant or a laminate for electrical/electronic substrates.
- the flame retardant curing agent for epoxy has excellent heat resistance, mechanical properties, moisture absorption resistance, and significantly improved electrical properties, as well as having flame retardant properties by including phosphorus element in the structure, by curing by including an epoxy resin It can be used for electrical/electronic encapsulants or electrical/electronic board laminates.
- epoxy resin known epoxy resins may be used within a range that does not impair the effects of the present invention.
- Epoxides of condensation resins epoxides of phenol aralkyl resins synthesized from phenols and paraxylylenedichloride, epoxides of biphenylaralkyl type phenol resins synthesized from phenols and bischloromethylbiphenyl, naphthols and para Epoxides of naphthol aralkyl resins synthesized from xylylene dichloride or the like may be used singly or in combination of two or more.
- the epoxy resin is ortho phenylphenol novolac epoxy, dicyclo It may include at least one selected from the group consisting of an epoxide type of a copolymer resin of pentadiene and phenols, an epoxide type of a biphenylaralkyl type phenolic resin synthesized from bischloromethyl biphenyl, etc.
- the laminated material may have a dielectric constant (Dk) of 3.0 or less and a dielectric loss of 0.01 or less at a frequency of 1 GHz, and such improved electrical insulation characteristics enable high-speed device integration through high integration of semiconductors on IC substrates and PCBs.
- Dk dielectric constant
- an inorganic filler may be mixed in addition to the epoxy resin and the curing agent according to the present invention to improve physical properties of the cured product.
- an inorganic filler When an inorganic filler is mixed, physical properties such as moisture absorption resistance may be improved, and when an inorganic filler is included, it may be suitable for encapsulation.
- the inorganic filler may be used without limitation inorganic fillers used in conventional electrical/electronic encapsulants or electrical/electronic board laminates, and non-limiting examples thereof include silica, alumina, zircon, calcium silicate, Calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, steatite, spinel, mullite, titania, etc. may be used, and these may be used singly or in combination of two or more. It is preferable, and as its form, a crushed shape or a spherical shape is mentioned. Silica is usually used in combination with several types of particle size distributions.
- the range of the average particle diameter of the silica which can be combined is preferably 0.5 ⁇ m to 100 ⁇ m, more preferably 1.5 ⁇ m to 50 ⁇ m.
- the content rate is preferably 83% by weight or more, more preferably 83 to 90% by weight. When it is less than 83% by weight, the content of organic components is high, and moisture resistance and low linear expansion may not be sufficiently exhibited.
- oligomers or high molecular compounds such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indencumarone resin, and phenoxy resin may be appropriately blended, and pigments, flame retardants, thixotropy Additives such as a imparting agent, a coupling agent, and a flow improver may be additionally blended.
- the pigment examples include organic or inorganic extender pigments and scale-like pigments.
- the thixotropy imparting agent include silicone-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, organic bentonite-based, and the like.
- curing accelerators such as amines, imidazoles, organic phosphines, and Lewis acids can be blended as necessary.
- the compounding amount of the curing accelerator is preferably 0.2 to 5 parts by weight, more preferably 1.0 to 4 parts by weight, based on 100 parts by weight of the epoxy resin.
- release agents such as carnauba wax and OP wax, coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane, colorants such as carbon black, flame retardants such as antimony trioxide, stress reducing agents such as silicone oil, Lubricants, such as calcium stearate, etc. can be mix
- An encapsulant according to a preferred embodiment of the present invention can be obtained by curing an encapsulant composition such as an epoxy resin or a flame retardant curing agent for epoxy according to the present invention by a molding method such as casting, compression molding, or transfer molding. Preferably, it can be obtained through transfer molding, and the temperature when the cured product is produced may be 120 to 220 °C.
- the compound represented by Formula 4 and the compound represented by Formula 3-1 were added in a molar ratio of 1:1.0 in the mixture, and the compound represented by Formula 4 and the endcapping agent were added in a 1:1.0 molar ratio in the mixture. was added in a molar ratio of
- the separated curing agent compound was subjected to vacuum degassing at 180 ° C. to obtain 610 g of a brown solid flame retardant curing agent for epoxy having a weight average molecular weight (Mw) of 2,921.
- n 1
- a curing agent was prepared in the same manner as in Example 1, but Example 2 was carried out using the compound represented by Formula 3-2 instead of the compound represented by Formula 3-1 as Compound 1.
- X 17 and X 18 are each independently , and n is 1.
- a curing agent was prepared in the same manner as in Example 1, but Example 3 was carried out using the compound represented by Formula 3-3 instead of the compound represented by Formula 3-1 as Compound 1.
- X 17 and X 18 are each independently an alkylene group having 1 carbon atom (-CH 2 -), and n is 1.
- a curing agent was prepared in the same manner as in Example 1, but Example 4 was carried out using the compound represented by Formula 4-2 instead of the compound represented by Formula 4-1 as Compound 2.
- a curing agent was prepared in the same manner as in Example 1, but Example 5 was carried out using the compound represented by Formula 4-3 instead of the compound represented by Formula 4-1 as Compound 2.
- E is to be.
- a curing agent was prepared in the same manner as in Example 1, but Example 6 was carried out using a compound represented by Formula 5-2 as a terminal blocker.
- a curing agent was prepared in the same manner as in Example 1, but Example 7 was carried out using a compound represented by Formula 5-3 as a terminal blocker.
- a curing agent was prepared in the same manner as in Example 1, but the molar ratio of the compound represented by Formula 4 (Compound 2) and the compound represented by Formula 3 (Compound 1, number of moles of phenolic hydroxyl groups (OH groups)) or the above Examples 8 to 11 and Comparative Examples 1 to 2 were performed with the molar ratio of the compound represented by Formula 4 (Compound 2) and the endcapping agent as shown in Tables 2 to 3 below.
- a curing agent was prepared in the same manner as in Example 1, but Comparative Examples 3 to 9 were prepared as shown in Table 4 below.
- Example 1 was analyzed through gel permeation chromatography (GPC, SHIMADZU) and infrared spectroscopy (IR), and the measurement result graphs are shown in FIGS. 1 and 2, respectively.
- the temperature of the column (KF-G, KF-801, KF-802, KF-803, KF-805) was set to 40 ° C, and the eluent was tetrahydrofuran (Tetraydrofuran, THF). ), and the flow rate (1 mL/min) and concentration (SAMPLE 0.1 g/THF 10 g, 20 ⁇ l injection) were measured.
- the molding operation was cured for 20 minutes at 180 ° C. and a pressure of 80 bar, and water After cooling was performed for 10 minutes using the same, post-curing was performed at 180° C. for 2 hours.
- a cured product was prepared in the same manner as in Preparation Example 1, but Preparation Examples 2 to 11 were performed using the curing agent prepared in Examples 2 to 11.
- a cured product was prepared in the same manner as in Preparation Example 1, but Comparative Preparation Examples 1 to 9 were performed using the curing agents prepared in Comparative Examples 1 to 9.
- the glass transition temperature (Tg) was measured using a differential thermal analyzer (DSC), and the 5% mass loss temperature (Td) of the cured product was cured after raising the temperature by 10°C per minute using a thermogravimetric analysis (TGA) device. The temperature when the weight loss of water is 5% was measured.
- DSC differential thermal analyzer
- Td 5% mass loss temperature
- the moisture absorption rate was measured as a weight increase rate (wt%) after the cured product was left in boiling water at 100° C. for 2 hours. The lower the moisture absorption, the better the physical properties of the cured product were evaluated.
- Peel strength was measured based on the GIS C-6417 method. The higher the peel strength, the better the mechanical strength was evaluated.
- CTE coefficient of thermal expansion
- the flame retardancy test was conducted according to the UL-94 method.
- V-0 grade If it is extinguished within 30 seconds and the cotton wool is not ignited by dropping.
- Class V-1 If it is extinguished within 60 seconds and the cotton wool is not ignited by the dropping.
- V-2 grade If it is extinguished within 60 seconds and the cotton wool is ignited by dropping
- Comparative Preparation Example 1 was found to have poor flame retardancy, through which it was confirmed that the molar ratio of the compounds represented by Formulas 3 and 4 of the present invention and the endcapping agent affect flame retardancy.
- Comparative Preparation Examples 3 to 9 which did not use the curing agent according to the present invention, had poor physical properties compared to those of Preparation Examples 1 to 11.
- Comparative Preparation Examples 3 to 9 which are cured products cured using the curing agents of Comparative Examples 3 to 9, such as Comparative Example 3, compared to Preparation Examples 1 to 11, the dielectric constant and It was confirmed that dielectric loss and moisture absorption were particularly high, and flame retardancy was also poor.
- Comparative Preparation Example 6 and Comparative Preparation Example 7 had not only a remarkably low glass transition temperature but also low peel strength and poor mechanical properties.
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- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
La présente invention concerne un agent durcissant ignifuge pour un époxy, et plus précisément, une composition d'agent durcissant ignifuge pour un époxy et un agent durcissant ignifuge qui est destiné à un époxy et qui la comprend, un produit durci obtenu au moyen de l'agent durcissant selon la présente invention ayant non seulement une température de transition vitreuse élevée, une faible absorption d'humidité, une excellente adhérence, une forte résistance au pelage et un faible coefficient de dilatation thermique, ainsi que des propriétés électriques remarquablement améliorées telles qu'en termes de constante diélectrique et de perte diélectrique, mais présentant également des propriétés ignifuges, et pouvant ainsi être largement utilisé dans les domaines de l'électricité et de l'électronique.
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KR1020210062286A KR102371132B1 (ko) | 2021-05-13 | 2021-05-13 | 에폭시용 난연성 경화제 조성물 및 이를 포함하는 에폭시용 난연성 경화제 |
KR10-2021-0062286 | 2021-05-13 |
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WO2022239955A1 true WO2022239955A1 (fr) | 2022-11-17 |
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PCT/KR2022/004079 WO2022239955A1 (fr) | 2021-05-13 | 2022-03-23 | Composition d'agent durcissant ignifuge pour époxy, et agent durcissant ignifuge pour époxy la comprenant |
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KR (1) | KR102371132B1 (fr) |
TW (1) | TWI797002B (fr) |
WO (1) | WO2022239955A1 (fr) |
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KR102371132B1 (ko) * | 2021-05-13 | 2022-03-11 | 주식회사 신아티앤씨 | 에폭시용 난연성 경화제 조성물 및 이를 포함하는 에폭시용 난연성 경화제 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20140067183A (ko) * | 2012-10-29 | 2014-06-05 | (주)우노 앤 컴퍼니 | 인 함유 공축합 수지 및 이를 이용한 난연성 조성물 |
KR101738968B1 (ko) * | 2016-09-23 | 2017-05-23 | 주식회사 신아티앤씨 | 에폭시용 경화제 및 이의 제조방법 |
KR20180084778A (ko) * | 2015-11-13 | 2018-07-25 | 아이씨엘-아이피 아메리카 아이엔씨. | 열경화성 수지용 활성 에스테르 경화제 화합물, 이를 포함하는 난연제 조성물 및 이로부터 제조된 물품 |
KR20200019618A (ko) * | 2017-06-21 | 2020-02-24 | 디아이씨 가부시끼가이샤 | 활성 에스테르 화합물 그리고 이것을 사용한 조성물 및 경화물 |
KR20200020696A (ko) * | 2017-06-21 | 2020-02-26 | 디아이씨 가부시끼가이샤 | 활성 에스테르 수지 그리고 이것을 사용한 조성물 및 경화물 |
KR102371132B1 (ko) * | 2021-05-13 | 2022-03-11 | 주식회사 신아티앤씨 | 에폭시용 난연성 경화제 조성물 및 이를 포함하는 에폭시용 난연성 경화제 |
Family Cites Families (4)
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KR101203150B1 (ko) | 2011-10-17 | 2012-11-21 | 인하대학교 산학협력단 | 신규 에폭시 수지, 그 제조방법 및 상기 에폭시 수지를 포함하는 에폭시 수지 조성물 |
KR101462309B1 (ko) | 2012-03-21 | 2014-11-14 | (주)엘지하우시스 | 아미노기 함유 인산에스테르 난연제 및 그 제조방법 |
KR101515488B1 (ko) * | 2014-07-01 | 2015-04-30 | 주식회사 신아티앤씨 | 에폭시용 경화제 |
CN106750226B (zh) * | 2014-11-11 | 2019-01-08 | 江苏雅克科技股份有限公司 | 含磷聚酯化合物组成及含磷阻燃环氧树脂固化物的制备方法 |
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2021
- 2021-05-13 KR KR1020210062286A patent/KR102371132B1/ko active IP Right Grant
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2022
- 2022-03-23 WO PCT/KR2022/004079 patent/WO2022239955A1/fr active Application Filing
- 2022-04-28 TW TW111116116A patent/TWI797002B/zh active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20140067183A (ko) * | 2012-10-29 | 2014-06-05 | (주)우노 앤 컴퍼니 | 인 함유 공축합 수지 및 이를 이용한 난연성 조성물 |
KR20180084778A (ko) * | 2015-11-13 | 2018-07-25 | 아이씨엘-아이피 아메리카 아이엔씨. | 열경화성 수지용 활성 에스테르 경화제 화합물, 이를 포함하는 난연제 조성물 및 이로부터 제조된 물품 |
KR101738968B1 (ko) * | 2016-09-23 | 2017-05-23 | 주식회사 신아티앤씨 | 에폭시용 경화제 및 이의 제조방법 |
KR20200019618A (ko) * | 2017-06-21 | 2020-02-24 | 디아이씨 가부시끼가이샤 | 활성 에스테르 화합물 그리고 이것을 사용한 조성물 및 경화물 |
KR20200020696A (ko) * | 2017-06-21 | 2020-02-26 | 디아이씨 가부시끼가이샤 | 활성 에스테르 수지 그리고 이것을 사용한 조성물 및 경화물 |
KR102371132B1 (ko) * | 2021-05-13 | 2022-03-11 | 주식회사 신아티앤씨 | 에폭시용 난연성 경화제 조성물 및 이를 포함하는 에폭시용 난연성 경화제 |
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TWI797002B (zh) | 2023-03-21 |
KR102371132B1 (ko) | 2022-03-11 |
TW202244103A (zh) | 2022-11-16 |
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