CN107915936A - Compound particle and its manufacture method - Google Patents
Compound particle and its manufacture method Download PDFInfo
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- CN107915936A CN107915936A CN201710238219.9A CN201710238219A CN107915936A CN 107915936 A CN107915936 A CN 107915936A CN 201710238219 A CN201710238219 A CN 201710238219A CN 107915936 A CN107915936 A CN 107915936A
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- epoxy resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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Abstract
The present invention provides a kind of compound particle and its manufacture method, can improve the dissolubility of polyvinyl methylal resin in the epoxy.The present invention can be by melting the punctulate polyvinyl methylal resin of tool, but is kneaded with liquid epoxy resin, and liquid epoxy resin is filled in the pore, so that as the compound particle and its manufacture method that are easily dissolved in epoxy resin.Liquid epoxy resin can be used a kind of liquid epoxy resin, is dissolved in by least two liquid epoxy resin persons of mixing or by least one solid epoxy resin at least one liquid epoxy resin and winner.
Description
Technical field
The present invention relates to a kind of deliquescent compound particle and its manufacture method improved in the epoxy.The compound grain
Son is that liquid is filled with the pore by being kneaded liquid epoxy resin in having punctulate polyvinyl formal particle
The particle of shape epoxy resin.
Background technology
The compound particle of the present invention can be used as the tough agent of epoxy resin.In addition, epoxy resin due to
Excellent cementability, intensity, heat resistance, engineering properties and electrical properties, so in bonding agent, coating, civil construction material, electricity
Widely used in the fields such as the matrix resin of gas electrical insulating material, sealing material and composite material.
Particularly in the case where using epoxy resin as the matrix resin of composite material, commonly using referred to as prepreg
Intermediate materials be molded, it is necessary to the characteristic such as sticky (tack), ductility (drape) of hanging down.And then also and for improve carbon fiber with
The purpose of the bonding of matrix resin, often allocates thermoplastic resin.Polyvinyl acetal class is usually used as thermoplastic resin,
Polyvinyl methylal resin represents for it.
In addition, to maintain the heat resistance of epoxy cure thing (glass transition temperature), and for the purpose of raising toughness,
There is a situation where the polyvinyl acetal class for being imported with carboxyl is equably compatible in the epoxy.In addition, as composite wood
Tough agent be represented as polyvinyl methylal resin come the polyvinyl acetal class used.In order to make polyvinyl contracting first
Urea formaldehyde is equably compatible in the epoxy, it is necessary to carry out more than 130 DEG C of heating, also worry dissolving step trouble, with
And the thermal history in the dissolving step.
[prior art literature]
[patent document]
[patent document 1] Japanese Patent Laid-fair 4-15253
[patent document 2] Japanese Patent Laid-fair 4-80054
[non-patent literature]
[non-patent literature 1] introduction epoxy resin volume 4 applies piece II pages 187, and Epoxy Resin Technology association compiles
The content of the invention
[the invention problem to be solved]
In order to obtain the effect of the Strengthening and Toughening of the epoxy cure thing as caused by polyvinyl methylal resin, it is necessary to make
Polyvinyl methylal resin is equably dissolved in epoxy resin.But polyvinyl methylal resin is being dissolved in epoxy
When in resin, it is necessary to be heated to 150 DEG C from 130 DEG C.Even if the problem of the present invention is below 120 DEG C, one kind is also provided in ring
The compound particle of favorable solubility in oxygen tree fat.
[means to solve the problem]
The present inventors, can be by not making tool in order to improve the dissolubility of polyvinyl methylal resin in the epoxy
Punctulate polyvinyl methylal resin melting, but be kneaded with liquid epoxy resin, and liquid ring is filled in the pore
Oxygen tree fat, can obtain the compound particle being easily dissolved in epoxy resin.
That is, the present invention is as described below.
[1] a kind of compound particle, is filled with component B in the pore of its particle in component A, and component A contain than
Example is 50 weight % to 99 weight %, and the content ratio of component B is 1 weight % to 50 weight %,
Component A：Polyvinyl methylal resin；
Component B：Liquid epoxy resin.
[2] the polyvinyl methylal resin of the compound particle as described in [1], wherein component A be include Component units a,
The compound of Component units b and Component units c,
Component units a
Component units b
Component units c.
[3] the polyvinyl methylal resin of the compound particle as described in [1] or [2], wherein component A is to further include composition
The compound of unit d,
Component units d
In the formula of Component units d, R1It independently is the alkyl of hydrogen or carbon number 1 to 5.
[4] the polyvinyl methylal resin of the compound particle as any one of [1] to [3], wherein component A is grain
Shape, and there is the pore volume of 0.1ml/g to 0.9ml/g in inside particles, particle diameter is 10 μm to 2000 μm.
[5] compound particle as any one of [1] to [4], wherein the liquid epoxy resin of component B is at 100 DEG C
For liquid.
[6] compound particle as any one of [1] to [5], the wherein liquid epoxy resin of component B are with least
The compound of 1 Oxyranyle.
[7] compound particle as any one of [1] to [6], the wherein liquid epoxy resin of component B are a kind of liquid
Epoxy resin, by least two liquid epoxy resin persons of mixing or by least one solid epoxy resin be dissolved in
Winner in a kind of few liquid epoxy resin.
[8] manufacture method of a kind of compound particle as any one of [1] to [7], it does not make as the poly- of A components
Vinyl methylal resin melts, but is kneaded with the liquid epoxy resin as B component.
[The effect of invention]
By means of the invention it is possible to provide a kind of polyvinyl methylal resin and ring that can be easily dissolved in epoxy resin
The compound particle and its manufacture method of oxygen tree fat.
Brief description of the drawings
Fig. 1 is 350 times of microphotograph of the polyvinyl methylal resin particle of A components.
Embodiment
The form of the present invention is compound particle.The compound particle is characterized in that：The punctulate polyvinyl contracting of tool is not made
Formaldehyde resin melts, but is kneaded with liquid epoxy resin, and fills liquid epoxy resin in the pore.
The compound particle of the present invention includes the polyvinyl methylal resin of component A and the liquid asphalt mixtures modified by epoxy resin of component B
Fat.Also reactive diluent can be included in component B.
The content of the polyvinyl methylal resin of component A in compound particle is 50 weight % to 99 weight %, preferably
For 70 weight % to 90 weight %.
In the case where the content of the polyvinyl methylal resin of component A is more than 50 weight %, the liquid ring of component B
The content of oxygen reduces, its compound can be operated with particle shape, and operability improves.And then due to reducing liquid-like constituents, so it is anti-
The only mutual caking of particle caused by the compound particle surface dissolving in preservation, will not become bulk, prevent in epoxy
Deliquescent decline in resin, therefore preferably.
In the case where the content of the polyvinyl methylal resin of component A is below 99 weight %, it can obtain and be used as this
The compound particle being easily dissolved in epoxy resin of the problem of invention, therefore preferably.
Content of the liquid epoxy resin of component B in compound particle is 1 weight % to 50 weight %, is preferably 10 weights
Measure % to 30 weight %.
In the case where the content of the epoxy resin of component B is below 50 weight %, its compound can be grasped with particle shape
Make, operability improves.And then in the case where the liquid epoxy resin of component B is more than 1 weight %, suppress compound in preservation
Particle surface dissolves, and prevents the mutual caking of particle, will not become bulk, prevent deliquescent decline in the epoxy,
Therefore preferably.
In the case where the content of the epoxy resin of component B is more than 1 weight %, can obtain as problem of the invention
The compound particle being easily dissolved in epoxy resin, therefore preferably.
The polyvinyl methylal resin of component A in the present invention is preferably comprising following Component units a, Component units
B, and Component units c.And then it can also include Component units d.
Component units a
Component units b
Component units c
Component units d
Relative to whole Component units, the Component units a to Component units d in the polyvinyl methylal resin of component A
Total containing ratio be preferably 80% to 100%.Other Component units that can be included in the polyvinyl methylal resin of component A
Intermolecular formal unit or hemiformal unit are included in example.Vinyl formal chain element beyond Component units a
Containing ratio is preferably less than 5mol%.
Component units a is the Component units with formal position, can pass through continuous polyvinyl alcohol chain element and formaldehyde
(HCHO) reaction and formed.
Component units b is the Component units for including vinyl acetate chain.
Component units c is the Component units for including vinyl alcohol chain.
Component units d is the chain with carboxyl, the R in chemical formula1The preferably alkyl of hydrogen or carbon number 1 to 5, more preferably
For hydrogen or the alkyl of carbon number 1 to 3.
In the polyvinyl methylal resin of component A, Component units a to Component units d can have systematicness and arrange (embedding
Section copolymer, alternate copolymer etc.), also can randomly it arrange (random copolymer), but be preferably randomly to arrange.
Each Component units in the polyvinyl methylal resin of component A are preferably：The containing ratio of Component units a is
The containing ratio of 49.9mol% to 80mol%, Component units b are 0.1mol% to 49.9mol%, and the containing ratio of Component units c is
0.1mol% to 49.9mol%, and the containing ratio of Component units d is 0mol% to 49.9mol%.More preferably：Component units a
Containing ratio be 49.9mol% to 80mol%, the containing ratio of Component units b is 1mol% to 30mol%, and Component units c's contains
It is 1mol% to 30mol% to have rate, and the containing ratio of Component units d is 0mol% to 30mol%.
In order to fully obtain chemical-resistant, pliability, abrasion performance, the machine of the polyvinyl methylal resin of component A
Tool intensity, is preferably set to more than 49.9mol% by the containing ratio of Component units a.In addition, the polyvinyl formal of component A
Component units a in resin is formed by the way that the vinyl alcohol chain point of continued presence in strand is carried out formalizing.That is, it is difficult
With by discontinuous vinyl alcohol chain in strand (such as between 2 vinyl formal chains clamping existing for 1 vinyl alcohol
Chain) carry out formalizing.Therefore, it is preferably that the containing ratio of Component units A is set to below 80.0mol% in synthesis.
If the containing ratio of Component units a is more than 0.1mol%, the polyvinyl methylal resin of component A is in solvent
Dissolubility or dissolubility in the epoxy become good.If setting the containing ratio of Component units b to 49.9mol%,
The chemical-resistant of the polyvinyl methylal resin of component A, pliability, abrasion performance, mechanical strength are difficult to decline, therefore excellent
Choosing.
In view of the dissolubility in solvent or dissolubility in the epoxy, Component units c is preferably by containing ratio
If to 49.9mol%.In addition, in the manufacture of the polyvinyl methylal resin of component A, when polyvinyl alcohol chain is carried out contracting first
During hydroformylation, Component units b and Component units c become equilibrium relation, thus the containing ratio of Component units c be preferably 0.1mol% with
On.
If dissolubility in view of good viscosity and in the epoxy, the containing ratio of Component units d is preferably to set
For below 49.9mol%.In addition, in order to be smoothed out by the cross-linking reaction of side chain carboxyl group and epoxy resin, and obtain not only
Heat resistance (glass transition temperature) is maintained, and the epoxy cure thing that obdurability is excellent, the containing ratio of Component units d are preferred
For more than 0.1mol%.
The weight average molecular weight of the polyvinyl methylal resin of component A is preferably 5000 to 300000, more preferably
10000 to 150000.
In the case where the weight average molecular weight of the polyvinyl methylal resin of component A is more than 5000, polyethylene
The dissolubility of base methylal resin in the epoxy improves, and obtains tough as caused by polyvinyl methylal resin
Change acts on, therefore preferably.On the other hand, in the case where weight average molecular weight is less than 300000, viscosity during dissolving is not
Can excessively it increase, for workability when shaping preferably.
The polyvinyl methylal resin of component A is granular, and most gaps (Fig. 1) are observed in particle.Preferably：
There is the pore volume of 0.1m1/g to 0.9ml/g in inside particles.
The compound particle of the present invention is obtained by including leaching liquid epoxy resin in the pore.By pre- in pore
Liquid epoxy resin is first filled, then the dissolubility in the case where making an addition in epoxy resin improves.
In addition, in the case where pore volume is more than 0.1ml/g, be readily available the present invention is easily dissolved in asphalt mixtures modified by epoxy resin
Compound particle in fat.In addition, the upper limit of pore volume is not particularly limited, it is preferably 0.9ml/g or so.
The polyvinyl methylal resin of component A is granular.Its particle diameter is preferably 10 μm to 2000 μm, more preferably
100 μm to 1500 μm.
If particle diameter is more than 10 μm, the table of the per unit mass of the polyvinyl methylal resin particle of component A
Area is insufficient, therefore the liquid epoxy resin of component B will not be attached to particle surface, but is fully impregnated in particle pore
In, in addition, the polyvinyl methylal resin particle surface there is no component A dissolved by the liquid epoxy resin of component B and
The situation for making compound particle lump, so as the compound particle that can be easily dissolved in epoxy resin, therefore preferably.
If particle diameter is less than 2000 μm, prevents the dissolving of compound particle in the epoxy from spending the time, become
As the compound particle being easily dissolved in epoxy resin of the feature of the present invention, therefore preferably.
The liquid epoxy resin of component B is preferably at least the epoxy resin of liquid at 100 DEG C, if in view of at room temperature
Operation, then more preferably at 25 DEG C be liquid epoxy resin.
If the temperature that the epoxy resin of component B becomes liquid is less than 100 DEG C, when the polyvinyl contracting first with component A
When urea formaldehyde mixes, the part that can inhibit the polyvinyl methylal resin melts in the epoxy, keeps compound particle,
Therefore preferably.
On the species of the liquid epoxy resin of component B, if being liquid at 100 DEG C, it is not particularly limited, but is preferably
The epoxy resin easily mixed with polyvinyl methylal resin.
In addition, the even epoxy resin of solid, if being mixed with liquid epoxy resin and being liquid at 100 DEG C,
It can be used in the present invention.
Epoxy resin is the compound for having in the molecule more than 2 epoxy groups, be can be used：Bisphenol-type epoxy resin, benzene
Phenol phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, glycidyl group amine type epoxy resin, isocyanates change
Property epoxy resin, urethane-modified epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin,
Dicyclopentadiene-type epoxy resin, fluorenes type epoxy resin etc..These epoxy resin can be used alone or and with it is two or more come
Use.
On bisphenol-type epoxy resin, have：Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-A D-ring oxygen tree
Fat, bisphenol-s epoxy resin, brominated bisphenol a type epoxy resin etc..
As bisphenol A type epoxy resin, included in limited company of Mitsubishi Chemical product：jER827、jER828、
jER834、jER1001、jER1002、jER1003、jER1004、jER1055、jER1007、jER1009、jER1010.DIC
(DIC) included in limited company's product：Love clone (Epiclon) 840, love clone (Epiclon) 850, love gram
Grand (Epiclon) 860, love clone (Epiclon) 1050, love clone (Epiclon) 1055, love clone (Epiclon)
2050th, love clone (Epiclon) 3050, Dongdu are melted into limited company's product and include：Albert (Epotohto) YD-
127th, Albert (Epotohto) YD-128, Albert (Epotohto) YD-134.
As bisphenol f type epoxy resin, included in limited company of Mitsubishi Chemical product：jER806、jER807、
JER4004P, jER4005P, jER4007P, jER4010P etc..DIC (DIC) limited company product includes love clone
(Epiclon) 830, Dongdu is melted into limited company's product and includes：Albert (Epotohto) YD-170, Albert
(Epotohto) YD-2001, Albert (Epotohto) YD-2004, Albert (Epotohto) YD-2005RL.
Bisphenol-s epoxy resin includes：The love clone (Epiclon) of DIC (DIC) limited company product
EXA-1514, love clone (Epiclon) EXA-1515 etc..
Brominated bisphenol a type epoxy resin includes：JER5046B80, jER of limited company of Mitsubishi Chemical product
5047B75, jER 5050T60, jER 5050, jER 5051, or the love of Japanese ink chemical industry limited company product
Clone (Epiclon) 152, love clone (Epiclon) 153 etc..
Phenol novolak type epoxy resin includes：JER152, jER154 of limited company of Mitsubishi Chemical product, or
Love clone (Epiclon) N-740 of DIC (DIC) limited company product, love clone (Epiclon) N-770, love
Clone (Epiclon) N-775；Dongdu chemical conversion limited company product includes Albert (Epotohto) YDPN-638 etc..
Cresol novolak type epoxy resin includes：The love clone of DIC (DIC) limited company product
(Epiclon) N-660, love clone (Epiclon) N-665, love clone (Epiclon) N-670, love clone
(Epiclon) N-673, love clone (Epiclon) N-695, or the EOCN-1020 of NIPPON PHARMACEUTICAL CO., LTD's product,
EOCN-102S, EOCN-104S etc..
Glycidyl group amine type epoxy resin includes：Sumitomo Chemical limited company product ELM-120, ELM-434,
ELM-434HV, love clone (Epiclon) 430-L of DIC (DIC) limited company product, love clone
(Epiclon) 430, or Albert (Epotohto) YH-434, the Albert of Dongdu chemical conversion limited company product
(Epotohto) YH-434L, or the jER604 of limited company of Mitsubishi Chemical product, or NIPPON PHARMACEUTICAL CO., LTD's system
GAN, GOT of product.
Isocyanate modified epoxy resin or urethane-modified epoxy resin include：The limited public affairs of Asahi Chemical Industry's epoxy share
Take charge of ACR1348 of AER4152 or Ai Dike (ADEKA) limited company product of product etc..
Alicyclic epoxy resin includes：Daicel chemical industry (Daicel Chemical Industries) share is limited
Sai Luo West Germany (Celloxide) 2021 of company's product, Sai Luo West Germany (Celloxide) 2080 etc..
Biphenyl type epoxy resin includes：The jER XY4000 of limited company of Mitsubishi Chemical product, jER YL6121H,
JER YL6640, or NC-3000 of NIPPON PHARMACEUTICAL CO., LTD's product etc..
Naphthalene type epoxy resin includes：The love clone (Epiclon) of DIC (DIC) limited company product
HP4032, or NC-7000, NC-7300 of NIPPON PHARMACEUTICAL CO., LTD's product etc..
Dicyclopentadiene-type epoxy resin includes：The love clone of DIC (DIC) limited company product
(Epiclon) HP7200, love clone (Epiclon) HP7200L, love clone (Epiclon) HP7200H, or Japanese chemical drug
XD-1000-1L, XD-1000-2L of limited company's product etc..
The liquid epoxy resin of component B is the compound with least one Oxyranyle, can also include reactivity dilution
Agent.Reactive diluent be preferably for more general epoxy resin molecular weight it is lower, and the viscosity at 25 DEG C for 2mPas extremely
100mPa·s。
By adding reactive diluent, the compound particle for being easier to be dissolved in epoxy resin can be obtained.In addition, pass through
Do not add in large quantities excessively, and suppress the melting of the polyvinyl formal particle surface of component A, prevent from making particle melt each other
Caking.
Reactive diluent has following compound as mono-epoxide species.
There are allyl glycidyl ether, n-butyl glycidyl ether, 2- hexyl glycidyl ethers, the higher alcohol of alcohol system
Glycidol ether.
Phenol system has：Phenyl glycidyl ether, to tert-butyl-phenyl glycidol ether, cresyl glycidyl ether, phenol
(EO)5Glycidol ether, secondary butyl phenenyl glycidol ether, anacardol diglycidyl ether, dibromo phenyl glycidol ether.
Other compounds have：Glycidyl methacrylate, styrene oxide, three-level carboxylic acid ethylene oxidic ester.
Reactive diluent has as diepoxide species：N, N '-diglycidylaniline, N, N- 2-glycidyls
Base-O- toluidines, hexahydrophthalic anhydride 2-glycidyl ester, polyethyleneglycol diglycidylether (n=2~13), second two
Alcohol diglycidyl ether, polypropylene glycol diglycidyl ether (n=3~11), neopentylglycol diglycidyl ether, 1,6- hexylene glycols
Diglycidyl ether, resorcinolformaldehyde resin, diglycidyl-O- phthalic acid esters, dibromoneopentyl glycol two
Glycidol ether.
Reactive diluent has as triepoxides class：Glycerine polyglycidyl ether, trimethylolpropane bunching water
Glycerin ether.
The liquid epoxy resin of component B can be used a kind of liquid epoxy resin or mix at least two epoxy resin
And winner.In addition, at least one solid epoxy resin can be also dissolved at least one liquid epoxy resin to use.
As long as each component of method that the epoxy resin of the polyvinyl methylal resin of component A and component B are kneaded can
The method being uniformly kneaded, is not particularly limited, and is preferably super mixer, ribbon blender, planetary-type mixer, kneading
Machine etc..
The temperature that the epoxy resin of the polyvinyl methylal resin of component A and component B are kneaded is preferably 0 DEG C to 100
℃.More preferably 20 DEG C to 50 DEG C.Kneading at room temperature is most suitable for for workability.
[embodiment]
Hereinafter, embodiments of the present invention are illustrated by embodiment, is an example person for representing embodiment, this
Invention is not only defined in embodiment.
In addition, the polyvinyl methylal resin that embodiment 1 is used to embodiment 4 and comparative example 1 into comparative example 2 is
JNC limited companies manufacture complete Buddhist nun Lake (Vinylec) (trade mark) PVF-K types (weight average molecular weight 50,
000) the polyvinyl methylal resin that, embodiment 5 and comparative example 3 are used into comparative example 4 is JNC limited companies system
The PVF-E types (weight average molecular weight 100,000) for the complete Buddhist nun Lake (Vinylec) (trade mark) made.On current evaluation
The average grain diameter of the middle batch used, PVF-K are 342 μm, and PVF-E is 717 μm.According to average grain diameter close to 342 μm of representative
The cross sectional photograph of particle is 0.71ml/g come the voidage for the pore obtained.
[embodiment 1]
<Utilize the manufacture of the compound particle of super mixer>
By polyvinyl methylal resin (complete Buddhist nun Lake (the Vinylec) (business of JNC limited companies manufacture of 2000g
Mark), grade：PVF-K) input is into super mixer, while be stirred with 1000rpm, while from the upper of super mixer
After the bisphenol A type epoxy resin (jER828 (trade mark) of limited company of Mitsubishi Chemical manufacture) of portion's addition 500g, in room temperature
Under continue stirring 15 minutes, manufacture compound particle.
<The solubility test of compound particle in the epoxy>
The manufactured compound particle of weighing 12.5g, making an addition to advance weighing has the jER828 (trade mark) of 87.5g
In 200mL beakers, using use for laboratory mixer, while being stirred with 120rpm, while confirming dissolubility at 90 DEG C.It is molten
The content of polyvinyl methylal resin in solution after solution becomes 10 weight %.
<Dissolve result>
When self-dissolving solution has started 90 minutes, the dissolving of compound particle can be confirmed.
[embodiment 2]
<Utilize the manufacture of the compound particle of super mixer>
By polyvinyl methylal resin (complete Buddhist nun Lake (the Vinylec) (business of JNC limited companies manufacture of 2000g
Mark), grade：PVF-K) input is into super mixer, while be stirred with 1000rpm, while from the upper of super mixer
The bisphenol A type epoxy resin (jER828 (trade mark) of limited company of Mitsubishi Chemical manufacture) of portion's addition 475g is reacted with being used as
Property diluent 25g 1,6- hexanediol diglycidyl ethers (long rapids chemical conversion (Nagase ChemteX) limited company's system
The pellet made receives Cauer (Denacol) EX212 (trade mark)) mixed liquor after, continue stirring 15 minutes at room temperature, manufacture compound grain
Son.
<The solubility test of compound particle in the epoxy>
The manufactured compound particle of weighing 12.5g, making an addition to advance weighing has the jER828 (trade mark) of 87.5g
In 200mL beakers, using use for laboratory mixer, while being stirred with 120rpm, while confirming dissolubility at 90 DEG C.It is molten
The content of polyvinyl methylal resin in solution after solution becomes 10 weight %.
<Dissolve result>
When self-dissolving solution has started 80 minutes, the dissolving of compound particle can be confirmed.
[embodiment 3]
<Utilize the manufacture of the compound particle of super mixer>
By polyvinyl methylal resin (complete Buddhist nun Lake (the Vinylec) (business of JNC limited companies manufacture of 2000g
Mark), grade：PVF-K) input is into super mixer, while be stirred with 1000rpm, while from the upper of super mixer
The bisphenol A type epoxy resin (jER828 (trade mark) of limited company of Mitsubishi Chemical manufacture) of portion's addition 450g is reacted with being used as
Property diluent 50g 1,6- hexanediol diglycidyl ethers (long rapids chemical conversion (Nagase ChemteX) limited company's system
The pellet made receives Cauer (Denacol) EX212 (trade mark)) mixed liquor after, continue stirring 15 minutes at room temperature, manufacture compound grain
Son.
<The solubility test of compound particle in the epoxy>
The manufactured compound particle of weighing 12.5g, making an addition to advance weighing has the jER828 (trade mark) of 87.5g
In 200mL beakers, using use for laboratory mixer, while being stirred with 120rpm, while confirming dissolubility at 90 DEG C.It is molten
The content of polyvinyl methylal resin in solution after solution becomes 10 weight %.
<Dissolve result>
When self-dissolving solution has started 70 minutes, the dissolving of compound particle can be confirmed.
[embodiment 4]
<Utilize the manufacture of the compound particle of super mixer>
By polyvinyl methylal resin (complete Buddhist nun Lake (the Vinylec) (business of JNC limited companies manufacture of 2000g
Mark), grade：PVF-K) input is into super mixer, while be stirred with 1000rpm, while from the upper of super mixer
The bisphenol A type epoxy resin (jER828 (trade mark) of limited company of Mitsubishi Chemical manufacture) of portion's addition 375g is reacted with being used as
Property diluent 125g 1,6- hexanediol diglycidyl ethers (long rapids chemical conversion (Nagase ChemteX) limited company's system
The pellet made receives Cauer (Denacol) EX212 (trade mark)) mixed liquor after, continue stirring 15 minutes at room temperature, manufacture compound grain
Son.
<The solubility test of compound particle in the epoxy>
The manufactured compound particle of weighing 12.5g, making an addition to advance weighing has the jER828 (trade mark) of 87.5g
In 200mL beakers, using use for laboratory mixer, while being stirred with 120rpm, while confirming dissolubility at 90 DEG C.It is molten
The content of polyvinyl methylal resin in solution after solution becomes 10 weight %.
<Dissolve result>
When self-dissolving solution has started 45 minutes, the dissolving of compound particle can be confirmed.
[embodiment 5]
<Utilize the manufacture of the compound particle of super mixer>
By polyvinyl methylal resin (complete Buddhist nun Lake (the Vinylec) (business of JNC limited companies manufacture of 2000g
Mark), grade：PVF-E) input is into super mixer, while be stirred with 1000rpm, while from the upper of super mixer
After the bisphenol A type epoxy resin (jER828 (trade mark) of limited company of Mitsubishi Chemical manufacture) of portion's addition 500g, in room temperature
Under continue stirring 15 minutes, manufacture compound particle.
<The solubility test of compound particle in the epoxy>
The manufactured compound particle of weighing 12.5g, making an addition to advance weighing has the jER828 (trade mark) of 87.5g
In 200mL beakers, using use for laboratory mixer, while being stirred with 120rpm, while confirming dissolubility at 120 DEG C.
The content of polyvinyl methylal resin in dissolved solution becomes 10 weight %.
<Dissolve result>
When self-dissolving solution has started 180 minutes, the dissolving of compound particle can be confirmed.
[comparative example 1]
<Compare particle>
Do not implement the blending with liquid epoxy resin using super mixer, but the polyvinyl contracting first of weighing 10g
Urea formaldehyde (the complete Buddhist nun Lake (Vinylec) (trade mark) of JNC limited companies manufacture, grade：PVF-K).
<Compare the solubility test of particle in the epoxy>
By the 10g polyvinyl methylal resins of weighing, making an addition to advance weighing has the jER828 (trade mark) of 90g
In 200mL beakers, using use for laboratory mixer, while being stirred with 120rpm, while confirming dissolubility at 90 DEG C.It is molten
The content of polyvinyl methylal resin in solution after solution becomes 10 weight %.
<Dissolve result>
After when 6 is small, the remaining of undissolved polyvinyl methylal resin is also confirmed.
[comparative example 2]
<Compare particle>
Do not implement the blending with liquid epoxy resin using super mixer, but the polyvinyl contracting first of weighing 10g
Urea formaldehyde (the complete Buddhist nun Lake (Vinylec) (trade mark) of JNC limited companies manufacture, grade：PVF-K).
<Compare the solubility test of particle in the epoxy>
By the 10g polyvinyl methylal resins of institute's weighing, making an addition to advance weighing has the jER828 (trade mark) of 90g
In 200mL beakers, using use for laboratory mixer, while being stirred with 120rpm, while confirming dissolubility at 130 DEG C.
The content of polyvinyl methylal resin in dissolved solution becomes 10 weight %.
<Dissolve result>
At 130 DEG C, when self-dissolving solution has started 90 minutes, the dissolving of polyvinyl methylal resin can be confirmed.
[comparative example 3]
<Compare particle>
Do not implement the blending with liquid epoxy resin using super mixer, but the polyvinyl contracting first of weighing 10g
Urea formaldehyde (the complete Buddhist nun Lake (Vinylec) (trade mark) of JNC limited companies manufacture, grade：PVF-E).
<Compare the solubility test of particle in the epoxy>
By the 10g polyvinyl methylal resins of institute's weighing, making an addition to advance weighing has the jER828 (trade mark) of 90g
In 200mL beakers, using use for laboratory mixer, while being stirred with 120rpm, while confirming dissolubility at 120 DEG C.
The content of polyvinyl methylal resin in dissolved solution becomes 10 weight %.
<Dissolve result>
After when 6 is small, the remaining of undissolved polyvinyl methylal resin is also confirmed.
[comparative example 4]
<Compare particle>
Do not implement the blending with liquid epoxy resin using super mixer, but the polyvinyl contracting first of weighing 10g
Urea formaldehyde (the complete Buddhist nun Lake (Vinylec) (trade mark) of JNC limited companies manufacture, grade：PVF-E).
<Compare the solubility test of particle in the epoxy>
By the 10g polyvinyl methylal resins of institute's weighing, making an addition to advance weighing has the jER828 (trade mark) of 90g
In 200mL beakers, using use for laboratory mixer, while being stirred with 120rpm, while confirming dissolubility at 150 DEG C.
The content of polyvinyl methylal resin in dissolved solution becomes 10 weight %.
<Dissolve result>
At 150 DEG C, when self-dissolving solution has started 180 minutes, the dissolving of polyvinyl methylal resin can be confirmed.
In table 1 experimental result is summarized into table 4.
1. embodiment 1 of table often closes particle composition and comparative example 1 to the polyvinyl formal of comparative example 2 to embodiment 4
Resin
The polyvinyl methylal resin of the compound particle composition and comparative example 3 to comparative example 4 of 2. embodiment 5 of table
3. embodiment 1 of table to embodiment 4 compound particle and comparative example 1 to comparative example 2 polyvinyl formal tree
The dissolubility evaluation result of fat in the epoxy
Dissolubility：Zero is dissolving.×：Dissolve insufficient.
*：Even if by 360 minutes, can not also dissolve.
The compound particle composition of 4. embodiment 5 of table is with the polyvinyl methylal resin of 3~comparative example of comparative example 4 in epoxy
Dissolubility evaluation result in resin
Dissolubility：Zero is dissolving.×：Dissolve insufficient.
*：Even if by 360 minutes, can not also dissolve.
It can be confirmed according to table 1 and table 3, compound particle (weight average molecular weight 50,000) and the comparative example 1 of embodiment
Polyvinyl methylal resin particle compare, the favorable solubility in the epoxy at 90 DEG C.In addition confirm, if increasing
Add the content of reactive diluent, then can shorten dissolution time.
It can be confirmed according to table 2 and table 4, compound particle (weight average molecular weight 100,000) and the comparative example 3 of embodiment
Polyvinyl methylal resin particle compare, the favorable solubility in the epoxy at 120 DEG C.
Understood in the case where weight average molecular weight is 50,000 polyvinyl methylal resin, such as comparative example 2
130 DEG C of solution temperature is needed, but by being set to the compound particle of the present invention, is then also dissolved at the temperature below 100 DEG C.
In addition, being understood in the case where weight average molecular weight is 100,000 polyvinyl methylal resin, such as compare
150 DEG C of solution temperature is needed as example 4, but by being set to the compound particle of the present invention, then it is also molten at a temperature of as low as 120 DEG C
Solution.
[industrial applicability]
The compound particle of the present invention can be applied as the tough agent of carbon fibre composite.
Claims (8)
- A kind of 1. compound particle, it is characterised in that：Component B, and the component A are filled with the pore of particle in component A Content ratio be that the content ratio of 50 weight % to 99 weight %, the component B is 1 weight % to 50 weight %,The component A：Polyvinyl methylal resin；The component B：Liquid epoxy resin.
- 2. compound particle according to claim 1, it is characterised in that：The polyvinyl methylal resin of the component A is Include the compound of Component units a, Component units b and Component units c,
- 3. compound particle according to claim 1 or 2, it is characterised in that：The polyvinyl methylal resin of the component A To further include the compound of Component units d,In the formula of Component units d, R1It independently is the alkyl of hydrogen or carbon number 1 to 5.
- 4. compound particle according to claim 1 or 2, it is characterised in that：The polyvinyl methylal resin of the component A To be granular, and there is the pore volume of 0.1ml/g to 0.9ml/g in inside particles, particle diameter is 10 μm to 2000 μm.
- 5. compound particle according to claim 1 or 2, it is characterised in that：The liquid epoxy resin of the component B at least exists It is liquid at 100 DEG C.
- 6. compound particle according to claim 1 or 2, it is characterised in that：The liquid epoxy resin of the component B be with The compound of at least one Oxyranyle.
- 7. compound particle according to claim 1 or 2, it is characterised in that：The liquid epoxy resin of the component B is one kind Liquid epoxy resin, by least two liquid epoxy resin persons of mixing or by least one solid epoxy resin dissolve The winner at least one liquid epoxy resin.
- A kind of 8. manufacture method of compound particle according to any one of claim 1 to 7, it is characterised in that：Do not make work Melt for the polyvinyl methylal resin of the A components, but be kneaded with the liquid epoxy resin as the B component.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016198920 | 2016-10-07 | ||
| JP2016-198920 | 2016-10-07 |
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|---|---|
| CN107915936A true CN107915936A (en) | 2018-04-17 |
| CN107915936B CN107915936B (en) | 2021-02-19 |
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| CN201710238219.9A Active CN107915936B (en) | 2016-10-07 | 2017-04-12 | Composite particle and method for producing same |
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|---|---|
| JP (1) | JP2018062643A (en) |
| CN (1) | CN107915936B (en) |
| TW (1) | TW201813999A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019202762A1 (en) * | 2018-04-20 | 2019-10-24 | Jnc株式会社 | Prepreg and fiber-reinforced composite material using same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4076626A (en) * | 1976-01-19 | 1978-02-28 | Union Carbide Corporation | High strength cast modules for supporting reverse osmosis membranes |
| JPS58108247A (en) * | 1981-12-21 | 1983-06-28 | Shikoku Chem Corp | Epoxy resin composition containing polyvinyl butyral resin |
| JP2002265621A (en) * | 2001-03-09 | 2002-09-18 | Japan U-Pica Co Ltd | Porous cured material and method for producing the same |
| JP2004244607A (en) * | 2002-12-20 | 2004-09-02 | Sk Kaken Co Ltd | Porous material |
| CN103467912A (en) * | 2013-08-08 | 2013-12-25 | 天津市凯华绝缘材料有限公司 | High flexibility epoxy resin composition |
-
2017
- 2017-04-12 CN CN201710238219.9A patent/CN107915936B/en active Active
- 2017-08-10 TW TW106127160A patent/TW201813999A/en unknown
- 2017-08-21 JP JP2017158773A patent/JP2018062643A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4076626A (en) * | 1976-01-19 | 1978-02-28 | Union Carbide Corporation | High strength cast modules for supporting reverse osmosis membranes |
| JPS58108247A (en) * | 1981-12-21 | 1983-06-28 | Shikoku Chem Corp | Epoxy resin composition containing polyvinyl butyral resin |
| JP2002265621A (en) * | 2001-03-09 | 2002-09-18 | Japan U-Pica Co Ltd | Porous cured material and method for producing the same |
| JP2004244607A (en) * | 2002-12-20 | 2004-09-02 | Sk Kaken Co Ltd | Porous material |
| CN103467912A (en) * | 2013-08-08 | 2013-12-25 | 天津市凯华绝缘材料有限公司 | High flexibility epoxy resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201813999A (en) | 2018-04-16 |
| CN107915936B (en) | 2021-02-19 |
| JP2018062643A (en) | 2018-04-19 |
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