CN101346218A - Molded foam article and method of producing molded foam article - Google Patents
Molded foam article and method of producing molded foam article Download PDFInfo
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- CN101346218A CN101346218A CNA2006800493483A CN200680049348A CN101346218A CN 101346218 A CN101346218 A CN 101346218A CN A2006800493483 A CNA2006800493483 A CN A2006800493483A CN 200680049348 A CN200680049348 A CN 200680049348A CN 101346218 A CN101346218 A CN 101346218A
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Abstract
It is intended to provide a molded foam article which has a high foaming ratio and a light weight and shows an excellent appearance with no surface coarsenss, and a method of producing a molded foam article whereby, in the case of using heat expandable microcapsules in injection molding, the heat expandable microcapsules can evenly expand to give a molded foam article having a high foaming ratio and an excellent appearance. A molded foam article having evenly distributed individual cells characterized in that the cell diameter is from 60 to 120 [mu]m, the specific gravity is 0.6 g/ml or less and the surface roughness is 4 [mu]m or less.
Description
Technical field
The present invention relates to expansion ratio height, lightweight and do not have shaggy manufacture method with foam molding and foam molding of excellent appearance, the manufacture method of described foam molding, even when in injection moulding, using the thermal expansivity micro-capsule, also carry out the foaming of thermal expansivity micro-capsule equably, the foam molding that can obtain the expansion ratio height thus, has excellent appearance.
Background technology
The variations such as state of the bubble of foamed resin by making raw material or formation can manifest various performances such as hiding hot, thermal insulation, sound insulation, sound absorption properties, shock resistance, lighting, so it can be used for various uses.As such foamed resin, for example use, the resin sheet that on the surface of Foamexes such as the polyurathamc by chemical foam blowing agent is obtained, expanded polypropylene, polyethylene foamed, foaming polychlorostyrene ethene, constitutes by polyvinyl chloride or olefin hydrocarbons thermoplasticity elastic body etc., or on such resin sheet, be fitted with padded coaming that composite molded product constituted of fabric etc. etc. as skin material.In addition, in recent years, not only proposed to be fitted with the foaming body of skin material, and proposed to contain the thermoplastic elastomer (TPE) of CBA and epidermis and move the foaming body that (cavity moving) method is carried out the subsidiary epidermis that injection moulding obtains by cavity with resin.
But, contain the shaping resin combination of CBA, even heating can not foamed yet sometimes, be used under the situation of injection moulding, blowing agent may sharply decompose etc. in forming machine, is difficult to handle.In addition, the kind according to the resin that uses can not obtain sufficient expansion ratio sometimes, can not obtain desired hardness as formed body.
Relative therewith, in the patent documentation 1, following purport is disclosed: the masterbatch pellet (maste batch pellets) that contains the ethene-alpha-olefin copolymer of CBAs such as azo-compound, nitroso compound, hydrazine derivate, bicarbonate by use, no matter the kind of resin how, it is high and form the injection expansion molding body of uniform bubble to obtain hardness and frothing percentage.
But the CBA that adds after the thermal decomposition all can produce the foaming residue at decomposition gas in any case simultaneously, and residue residual in formed body exerts an influence to the bond properties of formed body sometimes.In addition, if use the chemical blowing body, then there is following problem points: can all not become separated foam, all produce the part of continuous air bubbles in any case, thereby be difficult to obtain the very high foam molding of air-tightness.
As the reason that does not become separated foam, following reason is arranged: because the viscosity of resin is low excessively, the foaming power of decomposition gas surpasses the fusion tension force of resin, and the bubble wall of resin breaks as a result.Therefore, particularly to be applied in order to reduce the temperature of resin, improve its viscosity under the situation of injection molding method, need after resin being filled in the mould, make this resin cooling (mould discharges preceding cool time).
Relative therewith, in recent years, carried out the trial of using the thermal expansivity micro-capsule to replace CBA to make foam molding, for example, in patent documentation 2, put down in writing a kind of thermoplastic elastomer foaming body that utilizes the thermal expansivity micro-capsule that composition for thermoplastic elastomer is foamed and form, described composition for thermoplastic elastomer is by the radical crosslinking elastomer and thermoplastic resin constitutes and carry out crosslinked forming.
In addition, a kind of thermal expansivity micro-capsule is disclosed in patent documentation 3, it be to use by contain more than the nitrile monomer 80 weight %, below the nonnitriles monomer 20 weight % and the polymer that obtains of the polymerization composition of crosslinking agent 0.1～1 weight %, the thermal expansivity micro-capsule that volatile expanding agent is carried out microencapsulation and obtain, wherein, the nonnitriles monomer is methyl acrylic ester or esters of acrylic acid.
In addition, a kind of thermal expansivity micro-capsule that is made of shell polymeric and blowing agent is disclosed in patent documentation 4, described shell polymeric is made of the homopolymers or the copolymer that contain the ethylene unsaturated monomer more than the nitrile monomer 85 weight %, and described blowing agent contains more than the isooctane 50 weight %.
But, even use such thermal expansivity micro-capsule to make foam molding, be applied under the situation of injection moulding, can not obtain satisfied foam molding, the problem of facing has: can not obtain desired expansion ratio (proportion); Perhaps be shaped and occur distortion or bad order in the thing; Even perhaps obtain desired expansion ratio, also foam on the surface of formed products, thereby have rough surface, degraded appearance.
Patent documentation 1: TOHKEMY 2000-178372 communique
Patent documentation 2: Japanese kokai publication hei 11-343362 communique
Patent documentation 3: No. 2894990 specification of Japan Patent
Patent documentation 4: european patent application discloses specification No. 1149628
Summary of the invention
The object of the present invention is to provide the not coarse foam molding in expansion ratio height, lightweight and surface and the manufacture method of this foam molding with excellent appearance, manufacture method by described foam molding, even when in injection moulding, using the thermal expansivity micro-capsule, also carry out the foaming of thermal expansivity micro-capsule equably, thus the foam molding that can obtain the expansion ratio height and have excellent appearance.
The present invention is for having the foam molding of separated foam equably, and it is that 60～120 μ m, proportion are below the 0.6g/ml and surface roughness is the following foam moldings of 4 μ m for the aperture.
Below the present invention is described in detail.
Foam molding of the present invention has separated foam equably.Thus, excellences such as the lightweight of foam molding of the present invention, thermal insulation, resistance to impact, rigidity go for dwelling house with in the purposes such as building materials, automobile member, sole, can suit to use with member as automobile especially.
Be limited to 60 μ m on the aperture of foam molding of the present invention, be limited to 120 μ m down.
When less than 60 μ m, the hole is too small, can not satisfy the desired various performances of foam molding to thermal insulation, lighting etc., when surpassing 120 μ m, steep excessive, the intensity reduction of foam molding.Preferred be limited to 70 μ m down, be limited to 100 μ m on preferably.
In addition, above-mentioned aperture is the average maximum diameter of the bubble that exists in any part of foam molding, for example, observes the cross section of foam molding with microscope etc., and the mean value of maximum diameter that can be by calculating observed bubble is tried to achieve.
Be limited to 0.6g/ml on the proportion of foam molding of the present invention.When surpassing 0.6g/ml, can not satisfy the desired various performances of foam molding to thermal insulation, lighting etc.Be limited to 0.580g/ml on preferred.In addition, be limited to 0.480g/ml under preferred.
Above-mentioned proportion for example, can be measured according to the method that with JIS K-7112A method (displacement method in the water) is benchmark.
Be limited to 4 μ m on the surface roughness of foam molding of the present invention.When surpassing 4 μ m, the outward appearance of foam molding is significantly damaged.Be limited to 2 μ m on preferred.In addition, above-mentioned surface roughness is the maximum convex-concave (Japanese: the high さ in mountain), for example, according to being the method for benchmark with JIS B0601, measure by using the surface roughness profile measuring machine to wait of foaming and molding surface.
Foam molding of the present invention by lamination skin material from the teeth outwards, can obtain composite molded product, can be processed as 2 goods, 3 goods.
As above-mentioned skin material, can enumerate: leather, resin molding, weave cotton cloth, nonwoven etc.In addition, as above-mentioned skin material, also can use the subsidiary concavo-convex silicone pressing mold that forms by transfer printings such as natural leather, stone or wood etc., be formed in the composite molded product of designs such as having carried out hole skin or wooden hole pattern on the surface, in addition, also can form hard foamed layer in its surface, obtain the composite molded product of 3-tier architecture as aggregate.In addition, use metal as above-mentioned skin material, with respect to this metal, the composition that will contain matrix resin and thermal expansivity micro-capsule carries out injection moulding, can make the integrally formed type metal/resin of metal thus and be mixed into body.In addition, in the present invention, consider, preferably constitute by the thermoplastic elastomer (TPE) of homologous ray by foam molding foaming layer that constitutes and the epidermal area that constitutes by skin material from viewpoints such as recovery.
As the optimal way of foam molding of the present invention, for example can enumerate: little, the easy recovery of carrying capacity of environment, be widely used in dwelling house with building materials or automobile polyolefin formed body with member etc.
As above-mentioned automobile member, for example can enumerate: built-in material formed body, bumpers such as door trim, the instrument board stature material etc. of waiting for bus.In addition, also can be used for sole etc.
Foam molding of the present invention for example, can be made by the manufacture method of using the foam molding of the present invention shown in following.
The manufacture method of the present invention 1 foam molding, it is the method for making foam molding by injection moulding, this method has: with matrix resin and foaming initial temperature is that 160～180 ℃ thermal expansivity micro-capsule is heated to the temperature more than the foaming initial temperature of described thermal expansivity micro-capsule, the melting mixing operation of preparation molten mixture; And, described molten mixture is filled in the mould back open mold, thereby makes the foamed process of described thermal expansivity micro-capsule foaming, in described foamed process, making the time from the end-of-fill of described molten mixture to open mold is 2～4 seconds.
The manufacture method of the present invention 2 foam molding, it is the method for making foam molding by injection moulding, this method has: with matrix resin and foaming initial temperature is that 190～210 ℃ thermal expansivity micro-capsule is heated to the temperature more than the foaming initial temperature of described thermal expansivity micro-capsule, the melting mixing operation of preparation molten mixture; Described molten mixture is filled in the mould back open mold, thereby makes the foamed process of described thermal expansivity micro-capsule foaming, in described foamed process, making the time from the end-of-fill of described molten mixture to open mold is below 1 second.
The inventor has carried out deep research, found that, when the resin that use contains the thermal expansivity micro-capsule carries out injection moulding, can not obtain the former of formed body that the thermal expansivity micro-capsule foams fully because: long from the end-of-fill of molten mixture to the time of open mold, because the molten mixture after filling only periphery is cured, thereby form thick epidermal area, this epidermal area hinders the foaming of thermal expansivity micro-capsule.
And, the inventor has carried out more deep research, found that, by using the material of foaming initial temperature in prescribed limit as the thermal expansivity micro-capsule, and, make from the end-of-fill of molten mixture to open mold time within the limits prescribed, then carry out the foaming of thermal expansivity micro-capsule equably, can not form the epidermal area of necessary above thickness, thus, the foam molding that can obtain expansion ratio and mechanical strength height and have excellent outward appearance, thus the manufacture method of foam molding of the present invention finished.
The manufacture method of the present invention 1 foam molding has the melting mixing operation, wherein, with matrix resin and foaming initial temperature is that 160～180 ℃ thermal expansivity micro-capsule is heated to the temperature more than the foaming initial temperature of described thermal expansivity micro-capsule, makes molten mixture.
In the manufacture method of the present invention 1 foam molding, using the foaming initial temperature is 160～180 ℃ thermal expansivity micro-capsule.
In the manufacture method of the present invention 1 foam molding, the thermal expansivity micro-capsule that has the foaming initial temperature of above-mentioned scope by use, and mould is opened be set at the stipulated time, the foam molding that can obtain the expansion ratio height and have excellent appearance time delay as described later.
The preferred lower limit of the foaming initial temperature of above-mentioned thermal expansivity micro-capsule is 165 ℃, and preferred upper limit is 175 ℃.
In the manufacture method of the present invention 1 foam molding, by above-mentioned thermal expansivity micro-capsule being heated to the temperature more than the foaming initial temperature, after mould is opened,, can make the foaming of thermal expansivity micro-capsule by removing pressurized state, can obtain foam molding.In addition, in the manufacture method of the present invention 1 foam molding,, therefore can not foam to mould is open because the thermal expansivity micro-capsule is the state of pressurization.
In the manufacture method of the present invention 1 foam molding, the preferred lower limit of the maximum blowing temperature (Tmax) of above-mentioned thermal expansivity micro-capsule is 190 ℃.By Tmax being made as more than 190 ℃, can be reduced in tightening of thermal expansivity micro-capsule when putting into the thermal expansivity micro-capsule in the cylinder.
When being lower than 190 ℃, in cylinder, produce tightening of thermal expansivity micro-capsule, therefore, produce the decline of expansion ratio sometimes.
In addition, in this manual, maximum blowing temperature is meant when beginning from normal temperature to measure its diameter in the heat hot dilatancy micro-capsule, the temperature of (maximum displacement) when the diameter of thermal expansivity micro-capsule reaches maximum.
Above-mentioned thermal expansivity micro-capsule, the temperature that is preferably below the softening point that is included in shell in shell becomes the micro-capsule of the volatile expanding agent of gaseous state as the core agent, described shell be make contain that nitrile monomer 60 weight % are above, nonnitriles monomer 40 weight % following, the vinyl monomer composition of metal cation 0.1～10 weight % and crosslinking agent is polymerized.
By using such vinyl monomer composition and volatile expanding agent, can realize having Dmax, the Tmax of above-mentioned scope and the thermal expansivity micro-capsule of Ts.
As above-mentioned nitrile monomer, there is no particular limitation, for example can enumerate: acrylonitrile, methacrylonitrile, α-Lv Bingxijing, α-ethoxy propylene nitrile, flumaronitrile or their any mixture etc., preferably use acrylonitrile, methacrylonitrile.
In the manufacture method of the present invention 1 foam molding, the preferred lower limit of the content of above-mentioned nitrile monomer is 60 weight % in as the vinyl monomer composition of the raw material of above-mentioned shell.When being lower than 60 weight %, the barrier properties for gases of shell reduces, and therefore expansion ratio descends sometimes.
Be limited to 70 weight % under preferred, be limited to 80 weight % on preferred.
As above-mentioned nonnitriles monomer, be selected from: acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate, dicyclopentenyl acrylate; Methyl acrylic esters such as methyl methacrylate, EMA, butyl methacrylate, isobornyl methacrylate.Among them, be preferably methyl methacrylate, EMA, methyl acrylate especially.
The preferred upper limit of the content of nonnitriles monomer is 40 weight % in above-mentioned vinyl monomer composition.When surpassing 40 weight %, with above-mentioned same, the barrier properties for gases of shell reduces, and therefore expansion ratio descends sometimes.
Be limited to 30 weight % on preferred, be limited to 20 weight % under preferred.
Above-mentioned vinyl monomer composition preferably contains metal cation.Consider the vinyl monomer composition polymerization that contains above-mentioned metal cation by making, thereby above-mentioned metal cation and nonnitriles monomer react, resulting copolymer carries out ionomer, therefore, can obtain a kind of thermal expansivity micro-capsule, its hear resistance improves, and also can not cause at high-temperature area for a long time and break, shrinks.In addition, even at high-temperature area, the elastic modelling quantity of shell also is difficult to reduce, therefore, even under the situation that applies shaping processing such as the mixing shaping of strong shear strength, calendaring molding, extrusion molding, injection moulding, can not cause breaking, shrinking of thermal expansivity micro-capsule yet.
As above-mentioned metal cation, so long as can make it to carry out the metal cation of ionomer with the nonnitriles monomer reaction, just there is no particular limitation, for example can enumerate: Na, K, Li, Zn, Mg, Ca, Ba, Sr, Mn, Al, Ti, Ru, Fe, Ni, Cu, Cs, Sn, Cr, Pb plasma.Among them,, be preferably the ion of Zn especially preferably as Ca, the Zn of 2～3 valency metal cations, the ion of Al.These metal cations may be used alone, two or more kinds can also be used.
In addition, the combination when using above-mentioned metal cation more than 2 kinds, there is no particular limitation, but preferably alkali-metal ion and above-mentioned alkali metal metal cation in addition are used in combination.By having above-mentioned alkali-metal ion, can activate the functional group of vinyl monomer etc., promote metal cation beyond the above-mentioned alkali metal and the reaction between the above-mentioned carboxyl.As above-mentioned alkali metal, for example can enumerate: Na, K, Li etc.
The preferred lower limit of the content of the above-mentioned metal cation in above-mentioned vinyl monomer composition is 0.1 weight %, and preferred upper limit is 10 weight %.When being lower than 0.1 weight %, copolymer can not be carried out ionomer fully sometimes, the effect that can't obtain making hear resistance to improve, on the contrary, and when surpassing 10 weight %, the remarkable variation of foam characteristics sometimes.
Above-mentioned shell preferably contains crosslinking agent.By containing above-mentioned crosslinking agent, can strengthen the intensity of shell, hole wall is difficult to brokenly bubble when thermal expansion.
As above-mentioned crosslinking agent, be not particularly limited, can suit to use monomer usually with free-radical polymerised pair of key more than 2.As object lesson, for example can enumerate: divinylbenzene, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, molecular weight is two (methyl) acrylate of 200～600 polyethylene glycol, glycerine two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, oxirane modification trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, triallyl formal three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dihydroxymethyl-tristane two (methyl) acrylate etc.Among them, surpassing under 200 ℃ the high-temperature area, micro-capsule after the thermal expansion is difficult to shrink, keep the state after the expansion easily, therefore, be preferably the 2 functionality crosslinking agents such as two (methyl) acrylate of polyethylene glycol, more preferably 3 functionality crosslinking agents such as three of trimethylolpropane (methyl) acrylate.
The preferred lower limit of the content of the above-mentioned crosslinking agent in the above-mentioned shell is 0.1 weight %, is limited to 3 weight % on preferred.Be limited to 0.1 weight % under preferred, be limited to 1 weight % on preferred.
In addition, the shell of above-mentioned thermal expansivity micro-capsule, have segment and carboxyl from nitrile monomer, be preferably the shell of metal cation 0.1～10 weight % that contains following copolymer and 2～3 valencys, it is the segment of 3～8 free-radical polymerised unsaturated carboxylic acid monomer that described copolymer has from the carbon number of removing the ester residue.
It as the carbon number that has above-mentioned carboxyl and remove the ester residue 3～8 free-radical polymerised unsaturated carboxylic acid monomer, for example can use per molecule to have the monomer that is used for the free carboxy of ionomer more than 1, specifically for example can enumerate: unsaturated monocarboxylics such as acrylic acid, methacrylic acid, ethylacrylic acid, crotonic acid, cinnamic acid; The monoesters or derivatives thereof of unsaturated dicarboxylics such as unsaturated dicarboxylics such as maleic acid, itaconic acid, fumaric acid, citraconic acid, chloromaleic acid and acid anhydrides thereof or monomethyl maleate, ethyl maleate, butyl maleate, monomethyl fumarate, monomethyl ester, monomethyl itaconate, itaconic acid mono ethyl ester, itaconic acid mono.They may be used alone, two or more kinds can also be used.Among them, be preferably acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid especially.
In constituting the copolymer of above-mentioned shell, be that the preferred lower limit of content of the segment of 3～8 free-radical polymerised unsaturated carboxylic acid monomer is 10 weight % from the carbon number that has above-mentioned carboxyl and remove the ester residue, preferred upper limit is 50 weight %.When being lower than 10 weight %, maximum blowing temperature is below 180 ℃, and when surpassing 50 weight %, though maximum blowing temperature improves, expansion ratio descends, and is therefore not preferred.
Above-mentioned copolymer also can have as required except that from the segment of above-mentioned nitrile monomer and from the carbon number that has above-mentioned carboxyl and remove the ester residue being segment the segment of 3～8 free-radical polymerised unsaturated carboxylic acid monomer.As such segment, there is no particular limitation, for example can enumerate: from esters of acrylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, dicyclopentenyl acrylate, methyl acrylic esters such as methyl methacrylate, EMA, butyl methacrylate, isobornyl methacrylate, the segment of vinyl monomers such as vinyl acetate, styrene etc. etc.These monomers can suit to select to use according to the needed characteristic of thermal expansivity micro-capsule, but wherein preferably use methyl methacrylate, EMA, methyl acrylate etc.
Wherein, the content of such segment preferably is lower than 10 weight %.If be more than the 10 weight %, then the barrier properties for gases of shell reduces sometimes.
The preferred lower limit of the weight average molecular weight of above-mentioned copolymer is 100,000, and preferred upper limit is 2,000,000.If be lower than 100,000, then the intensity of shell descends sometimes, if surpass 2,000,000, then the intensity of shell becomes too high, and expansion ratio descends sometimes.
In above-mentioned thermal expansivity micro-capsule, the preferred lower limit of the degree of cross linking of above-mentioned shell is 75 weight %.If be lower than 75 weight %, then maximum sometimes blowing temperature reduces.
The above-mentioned degree of cross linking, free carboxy that comprise covalent bond sexual intercourse connection by crosslinking agent, has by above-mentioned polymer and above-mentioned metal cation carry out ionomer crosslinked the two.
In addition, in above-mentioned thermal expansivity micro-capsule, part or all of the free carboxy that above-mentioned polymer has carried out ionization, become carboxyl anion, because above-mentioned metal cation is formed ionic bond as counter cation (counter cation), therefore, can easily regulate the degree of cross linking by the content of above-mentioned metal cation.
In addition, for example when carrying out infrared absorption spectrometry, at 1500～1600cm
-1Near exist the asymmetric stretching motion by COO-to cause absorption, can confirm above-mentioned ionomer thus.
In above-mentioned thermal expansivity micro-capsule, the preferred lower limit of the degree of neutralization of above-mentioned shell is 5%.If be lower than 5%, then maximum sometimes blowing temperature reduces.
In addition, above-mentioned degree of neutralization is illustrated in the ratio of the carboxyl of above-mentioned metal cation combination in the free carboxy that above-mentioned copolymer has.
In addition, have in use under the situation of micro-capsule as above-mentioned thermal expansivity micro-capsule of following shell, preferably use the metal cation of 2～3 valencys as above-mentioned metal cation.Described shell contains the copolymer that has from the segment of above-mentioned nitrile monomer with from the carbon number of removing the ester residue with carboxyl the segment that is 3～8 free-radical polymerised unsaturated carboxylic acid monomer.
Consider the carboxyl reaction of the copolymer of above-mentioned metal cation and formation shell, copolymer carries out ionomer, therefore, can obtain a kind of thermal expansivity micro-capsule, and its hear resistance improves, and also can not cause for a long time at high-temperature area and break, shrinks.In addition, elastic modelling quantity at the high-temperature area lower casing also is difficult to reduce, therefore, even under the situation that applies shaping processing such as the mixing shaping of strong shear strength, calendaring molding, extrusion molding, injection moulding, can not cause breaking, shrinking of thermal expansivity micro-capsule yet.
The following 0.1 weight % that is limited to of the content of the above-mentioned metal cation in the above-mentioned shell, on be limited to 10 weight %.If be lower than 0.1 weight %, then can not make copolymer carry out ionomer fully, can't obtain making the effect of hear resistance raising, on the contrary, if surpass 10 weight %, the then remarkable variation of foam characteristics.
In addition, for carboxyl and the metal cation that above-mentioned copolymer is had moderately carries out ionomer, need regulate the amount of the metal cation of the free carboxy that each above-mentioned copolymer has according to the desired degree of cross linking, the preferred lower limit of metal cation amount, carboxylic acid amount with respect to above-mentioned copolymer is 0.01 times of mole, and preferred upper limit is 0.5 times of mole.If be lower than 0.01 times of mole, then the degree of cross linking does not improve, and is difficult to obtain effect on hear resistance.If surpass 0.5 times of mole, can not obtain its above effect even then cooperate.Be limited to 0.05 times of mole under preferred.
Above-mentioned shell can further contain stabilizing agent, ultra-violet absorber, antioxidant, antistatic agent, fire retardant, silane coupling agent, toner etc. as required.
Above-mentioned thermal expansivity micro-capsule comprises volatile expanding agent as the core agent in above-mentioned shell.
Above-mentioned volatile expanding agent is preferably the material that temperature below the softening point of the polymer that constitutes shell becomes gaseous state, is suitably low boiling point organic solvent.
As above-mentioned volatile expanding agent, for example can enumerate: low molecular weight hydrocarbons such as ethane, ethene, propane, propylene, normal butane, iso-butane, butylene, isobutene, pentane, isopentane, neopentane, n-hexane, heptane, benzinum; CCl
3F, CCl
2F
2, CClF
3, CClF
2-CClF
2Deng CFC; Tetraalkyl silane such as tetramethylsilane, trimethyl ethylsilane, trimethyl isopropyl silane, trimethyl n-pro-pyl silane etc.They can distinguish use separately, also can more than 2 kinds and use.
In the above-mentioned thermal expansivity micro-capsule, among above-mentioned volatile expanding agent, preferably using boiling point is hydrocarbon more than 60 ℃.By using such hydrocarbon, even under the high temperature when being shaped, high cutting condition, the thermal expansivity micro-capsule also is not easy to break, and can obtain the thermal expansivity micro-capsule of excellent heat resistance.
As above-mentioned boiling point is hydrocarbon more than 60 ℃, for example can enumerate: n-hexane, heptane, isooctane etc.Wherein be preferably heptane, isooctane.
In addition, the hydrocarbon with boiling point more than 60 ℃ can use separately separately, also can be lower than 60 ℃ hydrocarbon with boiling point and be used in combination.
In addition, as volatile expanding agent, can use by heating and carry out the thermal decomposition type compound that thermal decomposition forms gaseous state.
The preferred lower limit of the average grain diameter of above-mentioned thermal expansivity micro-capsule is 5 μ m, is limited to 100 μ m on preferred.If less than 5 μ m,,, then, therefore, have problems at aspects such as intensity sometimes because the bubble of resulting formed body is excessive if surpass 100 μ m then because the bubble of resulting formed body is too small, and therefore, the lighting of formed body sometimes is insufficient.Be limited to 10 μ m under preferred, be limited to 40 μ m on preferred.
In above-mentioned melting mixing operation, the preferred lower limit of the addition of above-mentioned thermal expansivity micro-capsule is 0.5 weight portion with respect to matrix resin 100 weight portions, is limited to 20 weight portions on preferred.If be lower than 0.5 weight portion, then the bubble of resulting formed body tails off, and can not bring into play various performances such as lighting.If surpass 20 weight portions, then sometimes in the aspects such as intensity of resulting formed body existing problems.
As the method for making above-mentioned thermal expansivity micro-capsule, there is no particular limitation, for example, can make by carrying out following operation.Described operation is: the operation of preparation aqueous medium; Make the oiliness mixed liquor be distributed to operation in the aqueous medium, the carbon number that described oiliness mixed liquor contains nitrile monomer, have carboxyl and remove the ester residue is 3～8 free-radical polymerised unsaturated carboxylic acid monomer and volatile expanding agent; Add the compound that generates metal cation, make the operation of above-mentioned carboxyl and metal cation reaction; And the operation that makes monomer polymerization by the heating dispersion liquid.
Under the situation of making above-mentioned thermal expansivity micro-capsule, prepare the operation of aqueous medium at first.As object lesson, for example, by add entry and dispersion stabilizer, as required auxiliary stabilizer in polymer reactor, preparation contains the aqueous dispersion medium of dispersion stabilizer.In addition, as required, also can add nitrite alkali slaine, stannous chloride, stannic chloride, potassium bichromate etc.
As above-mentioned dispersion stabilizer, for example can enumerate: silica, calcium phosphate, magnesium hydroxide, aluminium hydroxide, iron hydroxide, barium sulfate, calcium sulfate, sodium sulphate, calcium oxalate, calcium carbonate, calcium carbonate, brium carbonate, magnesium carbonate etc.
The addition of above-mentioned dispersion stabilizer, there is no particular limitation, waits according to the particle diameter of the kind of dispersion stabilizer, micro-capsule and suitablely determine, but with respect to monomer 100 weight portions, preferably is limited to 0.1 weight portion down, is limited to 20 weight portions on preferably.
As above-mentioned auxiliary stabilizer, for example can enumerate: the condensation product of the condensation product of diethanol amine and aliphatic dicarboxylic acid, urea and formaldehyde, polyvinylpyrrolidone, polyethylene glycol oxide, polymine, TMAH, gelatin, methylcellulose, polyvinyl alcohol, butanedioic acid di-isooctyl, sorbitan ester, various emulsifying agents etc.
In addition, combination as above-mentioned dispersion stabilizer and auxiliary stabilizer, be not particularly limited, for example can enumerate: the combination of the combination of the combination of cataloid and condensation product, cataloid and water-soluble nitrogen-containing compound, magnesium hydroxide and calcium phosphate and emulsifying agent etc.Among them, be preferably the combination of cataloid and condensation product.
In addition,, be preferably the condensation product of diethanol amine and aliphatic dicarboxylic acid, be preferably the condensation product of diethanol amine and adipic acid or the condensation product of diethanol amine and itaconic acid especially as above-mentioned condensation product.
As above-mentioned water-soluble nitrogen-containing compound, for example can enumerate: polyvinylpyrrolidone, polymine, polyoxyethylene alkyl amine, with polymethylacrylic acid dimethylaminoethyl or polyacrylic acid dimethylaminoethyl be the amino alkane ester of poly-(methyl) propenoic acid dialkyl of representative, with poly-dimethylamino propyl acrylamide or poly-dimethylamino-propyl Methacrylamide poly-diakyl aminoalkyl (methyl) acrylamide that is representative, polyacrylamide, polycation acrylamide, polyamine sulfone, polyallylamine etc.Among them, preferably use polyvinylpyrrolidone.
The addition of above-mentioned cataloid suits to determine according to the particle diameter of thermal expansivity micro-capsule, but with respect to vinyl monomer 100 weight portions, preferably is limited to 1 weight portion down, is limited to 20 weight portions on preferably.Be limited to 2 weight portions under preferred, be limited to 10 weight portions on preferred.For the amount of above-mentioned condensation product or water-soluble nitrogen-containing compound, suit to determine according to the particle diameter of thermal expansivity micro-capsule, but with respect to monomer 100 weight portions, preferably be limited to 0.05 weight portion down, be limited to 2 weight portions on preferably.
Except above-mentioned dispersion stabilizer and auxiliary stabilizer, can further add inorganic salts such as sodium chloride, sodium sulphate.By adding inorganic salts, can obtain having the thermal expansivity micro-capsule of shape of particle more uniformly.The addition of above-mentioned inorganic salts is preferably 0～100 weight portion with respect to monomer 100 weight portions usually.
The aqueous dispersion medium that contains above-mentioned dispersion stabilizer is dispersion stabilizer or auxiliary stabilizer to be mixed prepare in deionized water, and the pH of the water of this moment suit definite according to the kind of dispersion stabilizer that uses or auxiliary stabilizer.For example, when using silica such as cataloid as dispersion stabilizer, carrying out polymerization in acid medium, is acid in order to make aqueous medium, and adding acid such as hydrochloric acid as required, to come the pH of regulation system be 3～4.On the other hand, when using magnesium hydroxide or calcium phosphate, in alkaline medium, make its polymerization.
Afterwards, in the method for making the thermal expansivity micro-capsule, make following oiliness mixed liquor be distributed to operation in the aqueous medium, the carbon number that described oiliness mixed liquor contains nitrile monomer, have carboxyl and remove the ester residue is 3～8 free-radical polymerised unsaturated carboxylic acid monomer and volatile expanding agent.In this operation, monomer and volatile expanding agent can be added to respectively in the aqueous dispersion medium, preparation oiliness mixed liquor in aqueous dispersion medium, but in advance the two is mixed usually, make the oiliness mixed liquor after, add in the aqueous dispersion medium again.At this moment, preparation oiliness mixed liquor and aqueous dispersion medium in container separately stir in other container on one side in advance, Yi Bian mix, thus, the oiliness mixed liquor are dispersed in the aqueous dispersion medium, afterwards, add in the polymerization container.
For the above-mentioned monomer of polymerization, use polymerization initiator, above-mentioned polymerization initiator can add in the above-mentioned oiliness mixed liquor in advance, adds after also can be in polymerization container aqueous dispersion medium and oiliness mixed liquor being mixed.
As above-mentioned polymerization initiator, there is no particular limitation, for example can suit to use: dissolve in the dialkyl peroxide, diacyl peroxide, peroxyester, peroxy dicarbonate, azo-compound of above-mentioned monomer etc.As object lesson, for example can enumerate: dialkyl peroxides such as Methylethyl peroxide, di-tert-butyl peroxide, dicumyl peroxide; Isobutyl peroxide, benzoyl peroxide, 2,4-dichloro-benzoyl base peroxide, 3,5, diacyl peroxides such as 5-trimethyl acetyl peroxide; Cross the neopentanoic acid tert-butyl ester, cross the own ester of neopentanoic acid uncle, cross the neodecanoic acid tert-butyl ester, cross the own ester of neodecanoic acid uncle, cross neodecanoic acid 1-cyclohexyl-1-methyl ethyl ester, cross neodecanoic acid 1,1,3, peroxyesters such as 3-tetramethyl butyl ester, the withered ester of peroxidating neodecanoic acid, (α, α-two new caprinoyl peroxides) diisopropyl ester benzene; Peroxy dicarbonates such as two (4-tert-butylcyclohexyl) peroxy dicarbonate, di peroxy dicarbonate, diisopropyl peroxydicarbonate, two (peroxidating of 2-ethyl diethyldithiocarbamate) two carbonic esters, dimethoxy butyl peroxyization two carbonic esters, two (3-methyl-3-methoxyl group butyl peroxyization) two carbonic esters; 2,2 '-azodiisobutyronitrile, 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 1,1 '-azo two azo-compounds such as (1-cyclohexanenitriles) etc.
As the particle diameter method that emulsification disperses in aqueous dispersion medium that makes above-mentioned oiliness mixed liquor with regulation, can enumerate: carry out stirring method or make its method of passing through silent oscillation dispersal devices such as pipe-line mixer or component type silent oscillation disperser etc. by homogenizer (for example, special machine chemical industry corporate system) etc.
In addition, water system decentralized medium and polymerism mixture can be supplied to respectively in the above-mentioned silent oscillation dispersal device, also can supply with the dispersion liquid after being pre-mixed, stirring.
Then, in the method for making the thermal expansivity micro-capsule, add the compound that generates metal cation (below be also referred to as metal cation supply with body), the operation that above-mentioned carboxyl and metal cation are reacted.By carrying out this operation, above-mentioned metal cation and carboxyl reaction are carried out ionomer, thus, can make a kind of thermal expansivity micro-capsule, and its hear resistance improves, and also can not cause for a long time under high-temperature area and break, shrinks.In addition, because the raising of the elastic modelling quantity of above-mentioned shell, therefore, even under the situation that applies shaping processing such as the mixing shaping of strong shear strength, calendaring molding, extrusion molding, injection moulding, can not cause breaking, shrinking of thermal expansivity micro-capsule yet.
Above-mentioned metal cation is supplied with body, can add to make in the above-mentioned monomer polymerization dispersion liquid before, also can add after above-mentioned monomer polymerization.In addition, above-mentioned metal cation is supplied with body, can directly add itself, also can add with the form of solution such as the aqueous solution.
Supply with body as above-mentioned metal cation, there is no particular limitation, for example can enumerate: each organic acid salt such as the oxide of above-mentioned metal cation, hydroxide, phosphate, carbonate, nitrate, sulfate, chloride, nitrite, sulphite or caprylic acid, stearic acid etc. etc.Among them, be preferably hydroxide, chloride, carboxylate.Particularly, be preferably Zn (OH)
2, ZnO, Mg (OH)
2Deng, reduce and consider from reducing elastic modelling quantity under high-temperature area, more preferably Zn (OH)
2
In addition, under the situation of adding above-mentioned metal cation supply body, be preferably: after adding alkali-metal hydroxide in advance, add above-mentioned alkali-metal hydroxide metal cation in addition and supply with body.By adding above-mentioned alkali-metal hydroxide in advance, can activated carboxyl etc. functional group, promote reaction with above-mentioned metal cation.In addition, Zn (OH)
2Water-soluble low, can not obtain desired ionomer by adding sometimes, but, for example,, to add the high ZnCl of the aqueous solution by after adding NaOH by using such method
2, also can obtain and add Zn (OH)
2The identical effect of situation.
As above-mentioned alkali-metal hydroxide, there is no particular limitation, is preferably the hydroxide of Na, K, Li, the wherein preferred strong Na of alkalescence, the hydroxide of K of using.
Above-mentioned thermal expansivity micro-capsule can be made by following operation, and described operation is: will heat through the dispersion liquid that above-mentioned operation obtains, make monomer polymerization thus.The maximum blowing temperature height of the thermal expansivity micro-capsule that obtains by such method manufacturing, excellent heat resistance adds in high-temperature area or shaping and also can not break man-hour, to shrink.
As above-mentioned matrix resin, there is no particular limitation, for example can enumerate: polyurethane resin, the epoxy resin that contains thermosetting epoxy resin, ethene-alpha-olefin copolymer, ethlyene dichloride resinoid etc.Wherein, the thermal expansivity micro-capsule after the expansion can shrink once more by being heated to high temperature, " tightens that (Japanese: へ り) viewpoint of " phenomenon is considered, is preferably ethene-alpha-olefin copolymer from can effectively preventing to be called as.
As above-mentioned ethene-alpha-olefin copolymer, can use commercially available product, as commercially available product, for example can enumerate: " エ Application ゲ one ジ (DuPont Dow Elastomers elastomer Japanese firm system) " etc.Above-mentioned ethene-alpha-olefin copolymer can use separately, also can use with the form of mixture by polypropylene.Therefore the excellent dispersion of above-mentioned ethene-alpha-olefin copolymer in polypropylene, can improve polyacrylic modulus properties with EP rubber phase ratio.Thus, with the mixture of polypropylene and ethene-alpha-olefin copolymer during as matrix resin, slimming easily.
In addition, above-mentioned ethene-alpha-olefin copolymer may be used alone, two or more kinds can also be used.
When using above-mentioned ethene-alpha-olefin copolymer as above-mentioned matrix resin, the highest fusion peak temperature Tmax that above-mentioned ethene-alpha-olefin copolymer obtains by differential scanning calorimetry (DSC) (DSC) (℃) preferred lower limit be 60 ℃, preferred upper limit is 100 ℃.If surpass 100 ℃, the resin combination that then contains above-mentioned ethene-alpha-olefin copolymer is difficult to process sometimes.Be limited to 60 ℃ under preferred, be limited to 80 ℃ on preferred.
Above-mentioned ethene-alpha-olefin copolymer also can mix with other olefin hydrocarbons thermoplasticity elastic body and uses.At this moment, as the content of above-mentioned ethene-alpha-olefin copolymer,, be 60～100 weight % then with respect to masterbatch integral body if only consider foaminess when using as masterbatch (master batch), more preferably 80～100 weight % are preferably 100 weight % especially.
According to the kind of above-mentioned matrix resin, determine that resulting foam molding is soft foamed material or hard foam.That is, when using soft resin as above-mentioned matrix resin, resulting foam molding is a soft foamed material, and when using hard resin as above-mentioned matrix resin, resulting foam molding is a hard foam.
Obtain the matrix resin of soft foamed material, can enumerate: the thermoplastic elastomer (TPE) of olefines, polyurethanes or phenylethylene.In the above-mentioned olefin hydrocarbons thermoplasticity elastic body, as commercially available product, for example can enumerate: " エ Application ゲ one ジ " series (DuPont Dow Elastomers elastomer Japanese firm system), " ミ ラ ス ト マ one " series (Mitsui Chemicals corporate system), " Sumitomo TPE Santoprene " series (sumitomo chemical company system), " Santoprene " series (AES corporate system) etc.In addition, as the vinyl elastomer, can enumerate " Rabalon " series of Mitsubishi Chemical Ind's manufacturing etc.In addition, the processability or the hardness of cooperation expectation can be with these resin mixing uses.
Obtain the matrix resin of hard foam, can enumerate: PP type, acrylonitrile-butadiene-ethylene copolymer (ABS), phenylethylene, crylic acid resin, vinyl cyanide resin etc.In addition, as commercially available product, for example can enumerate: HOPP resin " PF814 " (MontellPolyolefines (covering special record polyolefin) corporate system), random polypropylene resin " B230 " " J704 " (Grand Polymer (Ge Lang specialization) corporate system), high density polyethylene (HDPE) " 3300F " (Mitsui Chemicals corporate system) etc.In addition, these resins can mix use.
In addition, above-mentioned matrix resin can be the degradability resin, for example can enumerate: as cellulose acetate (P-CA) resinoid or polycaprolactone (P-H, P-HB) resinoid " Cell Green " series (Daicel chemical industrial company system), PLA " LACEA " (Mitsui Chemicals corporate system) etc.In the manufacture method of the present invention 1 foam molding,, can use a kind of degradability resin separately according to thermal characteristics, perhaps mix more than 2 kinds and use, in addition, also above-mentioned degradability resin can be used separately, perhaps with above-mentioned degradability resin other matrix resins and usefulness in addition.
In the manufacture method of the present invention 1 foam molding, the foaming and molding body and function resin combination that contains above-mentioned matrix resin and thermal expansivity micro-capsule can be used as masterbatch pellet.
As the method for making above-mentioned masterbatch pellet; there is no particular limitation, for example, can enumerate following method etc.; described method is: it is mixing in advance to use in the same way two-way extruder etc. to carry out raw material such as matrix resins such as thermoplastic resin, various additives; afterwards, be heated to set point of temperature, after the blowing agents such as interpolation thermal expansivity micro-capsule; to obtain mixing thing by further mixing; with comminutor the mixing thing of gained is cut to the size of expectation, becomes grain shape thus, obtain masterbatch pellet.In addition, with raw material such as matrix resins such as thermoplastic resin or thermal expansivity micro-capsule with batch-type mixer carry out mixing after, carry out granulation with comminutor, can make the masterbatch pellet of grain shape thus.
As above-mentioned mixing roll, carry out mixing mixing roll so long as can not destroy the thermal expansivity micro-capsule, then there is no particular limitation, for example, can enumerate: pressurization kneading machine, closed mixing machine etc.
The manufacture method of the present invention 1 foam molding has the foamed process that makes above-mentioned thermal expansivity micro-capsule foaming after being filled to above-mentioned molten mixture in the mould by open mold.By carrying out such operation, can make foamed state evenly and obtain tiny separated foam, thereby can make foam molding with excellent appearance.
At this, an example of the fill method in the above-mentioned foamed process, foaming method etc. is shown among Fig. 1.
In above-mentioned foamed process, at first,, fill the molten mixture (Fig. 1 (a)) of thermal expansivity micro-capsule and matrix resin by at the casting nozzle 1 of mould as the cavity side formation of fixation side.
Afterwards, behind the end-of-fill (Fig. 1 (b)) of molten mixture, by pulling out core 2, open mold interior (Fig. 1 (c)).
Then, make the thermal expansivity micro-capsule foaming (Fig. 1 (d)) that molten mixture inside contains after, make matrix resin solidify (Fig. 1 (e)), make foam molding thus.In the manufacture method of the present invention 1 foam molding, because the thermal expansivity micro-capsule plays the same effect of meteorologic balloon, therefore, for the fusion tension force that in the shaping of the foam molding that uses CBA, becomes the matrix resin of problem, needn't consider, after filling molten mixture, open mold immediately.
In the manufacture method of the present invention 1 foam molding, the following of time (below be also referred to as mould open time delay) that begins to mould open (Fig. 1 (c)) from the end-of-fill (Fig. 1 (b)) of above-mentioned molten mixture is limited to 2 seconds, on be limited to 4 seconds.
In the manufacture method of the present invention 1 foam molding, use foaming initial temperature is 160～180 ℃ a thermal expansivity micro-capsule, by mould was made as 2～4 seconds open time delay, then carry out the foaming of thermal expansivity micro-capsule equably in addition, can not form the epidermal area of necessary above thickness, thus, obtain a kind of foam molding, its expansion ratio height, and form desired epidermal area, suppress foaming on the formed products surface, therefore have excellent outward appearance.
In addition, the thermally foamable micro-capsule plays the same effect of meteorologic balloon during foaming, can not produce gas at once, and therefore different with the situation of using CBA to form, the melt viscosity of resin also can be low.
If above-mentioned mould open time delay of less than 2 seconds, the rough surface of resulting foam molding then, degraded appearance.If surpass 4 seconds, then form the epidermal area of necessary above thickness, the thermal expansivity micro-capsule is foamed state not.
In above-mentioned foamed process, as being used to make mould is 2～4 seconds concrete grammar open time delay, for example can enumerate the method for using the device with following mechanism, described mechanism is: detect the testing agency of the end-of-fill of molten mixture, according to from the open controlling organization of the information control mould of testing agency and according to from the open mechanism of the signal of the above-mentioned controlling organization mould that mould is open.
As above-mentioned testing agency, for example in injection process, can enumerate: the mechanism of detecting the end-of-fill of molten mixture according to the position of the screw rod of injection machine; The position of stipulating in mould is provided with pressure sensor, and will fills mechanism that molten mixture detects as signal etc. on this position.
The preferred lower limit of the mold temperature in the above-mentioned foamed process is 40 ℃.If be lower than 40 ℃, then the cooling velocity of molten mixture becomes too fast, and the thermal expansivity micro-capsule becomes not foamed state, and is remaining sometimes.
The manufacture method of the present invention 2 foam molding, it is the method for making foam molding by injection moulding, this method has: the melting mixing operation, wherein, be that the temperature that 190～210 ℃ thermal expansivity micro-capsule is heated to more than the foaming initial temperature of described thermal expansivity micro-capsule is made molten mixture with matrix resin and foaming initial temperature; Foamed process, wherein be filled to described molten mixture in the mould after, by open mold, make the foaming of described thermal expansivity micro-capsule; And in described foamed process, making the time from the end-of-fill of described molten mixture to open mold is below 1 second.
In the manufacture method of the present invention 2 foam molding, the following of the foaming initial temperature of the thermal expansivity micro-capsule of use is limited to 190 ℃, on be limited to 210 ℃.In the manufacture method of the present invention 2 foam molding, by being opened, mould is set in above-mentioned scope time delay, even then use foaming initial temperature is 190～210 ℃ a thermal expansivity micro-capsule, also can obtain a kind of foam molding, it can not form the epidermal area of necessary above thickness, the expansion ratio height, and, therefore have excellent outward appearance owing to suppress foaming on the formed products surface.
Preferred be limited to 195 ℃ down, be limited to 205 ℃ on preferably.
In the manufacture method of the present invention 2 foam molding, the preferred lower limit of the maximum blowing temperature (Tmax) of above-mentioned thermal expansivity micro-capsule is 210 ℃.By Tmax being made as more than 210 ℃, can reduce tightening of thermal expansivity micro-capsule when putting into the thermal expansivity micro-capsule in the cylinder.
If be lower than 210 ℃, then in cylinder, produce tightening of thermal expansivity micro-capsule, therefore, produce the decline of expansion ratio sometimes.
In the manufacture method of the present invention 2 foam molding, be limited to 1 second to the open time of mould (open time delay of mould) from the end-of-fill of described molten mixture.
In the manufacture method of the present invention 2 foam molding, when to use the foaming initial temperature be 190～210 ℃ thermal expansivity micro-capsule, by being opened, mould is set at below 1 second time delay, can carry out the foaming of thermal expansivity micro-capsule equably, can not form the epidermal area of necessary above thickness, obtain a kind of foam molding thus, its expansion ratio height, and form the epidermal area of expectation,, therefore have excellent outward appearance owing to suppress foaming on the formed products surface.
In addition, the thermally foamable micro-capsule plays the same effect of meteorologic balloon during foaming, can not produce gas at once, and therefore different with the situation of using CBA to form, the melt viscosity of resin also can be low.
If above-mentioned mould surpasses 1 second open time delay, then form the epidermal area of necessary above thickness, the thermal expansivity micro-capsule becomes not foamed state.Be limited to 0.5 second on preferred.In addition, there is no particular limitation for the lower limit of above-mentioned mould open time delay, but consider from the restriction of machinery, is about 0.01 second on the reality.
In above-mentioned foamed process, make mould open the concrete grammar that foreshortens to time delay below 1 second as being used to, for example, can enumerate the method for using device with following mechanism, described mechanism is: the testing agency of detecting the end-of-fill of molten mixture; According to information, the open controlling organization of control mould from testing agency; And according to opening mechanism from the signal of above-mentioned controlling organization, the mould that mould is open.
As above-mentioned testing agency, for example can enumerate: the position of screw rod is detected and is reached the time that resin fills or the position of stipulating in mould pressure sensor, and mechanism that will potting resin detects as signal on this position are set when the injection process of injection machine.
According to the signal that is obtained by above-mentioned testing agency, as above-mentioned controlling organization or the open mechanism of mould, by the mechanism of direct use injection machine, can make mould open time delay is below 1 second.
For matrix resin that in the manufacture method of the present invention 2 foam molding, uses etc., identical with the situation of the manufacture method of the present invention 1 foam molding, therefore, omit its detailed explanation.
But, about volatile expanding agent, to use more than 2 kinds, the difference of preferably using the boiling point of the highest volatile expanding agent of minimum volatile expanding agent of boiling point and boiling point is the volatile expanding agent more than 60 ℃.Thus, can be implemented in interior the tightening of thermal expansivity micro-capsule of cylinder simultaneously prevents and the foaminess in mould.As these combinations, for example can enumerate: the combination of isopentane and isooctane etc.
According to the present invention, expansion ratio height, lightweight can be provided and not have shaggy manufacture method with foam molding and this foam molding of excellent appearance, manufacture method by described foam molding, even when in injection moulding, using the thermal expansivity micro-capsule, also carry out the foaming of thermal expansivity micro-capsule equably, thus the foam molding that can obtain the expansion ratio height and have excellent appearance.
Description of drawings
Fig. 1 is the schematic diagram of an example of explanation foamed process of the present invention.
The specific embodiment
By the following examples the present invention is described in more details, but the present invention is not limited in these embodiment.
Embodiment
(embodiment 1～8, comparative example 1～19)
(manufacturing of thermal expansivity micro-capsule)
Water 8L, cataloid (rising sun electrification corporate system) 10 weight portions are put in the polymerization container preparation aqueous dispersion medium as dispersion stabilizer and polyvinylpyrrolidone (BASF AG's system) 0.3 weight portion.Afterwards, in aqueous dispersion medium, add the oiliness mixed liquor that monomer, crosslinking agent, volatile expanding agent and polymerization initiator by the use level shown in the table 1 constitute, further add the metal cation of the use level shown in the table 1 and give body, prepare dispersion liquid thus.Resulting dispersion liquid is mixed with homogenizer, be encased in the pressure polymerization pot (20L) behind the nitrogen replacement, pressurize (0.2MPa) makes its reaction 20 hours, thus the preparation feedback product under 60 ℃.Reaction products resulting is filtered repeatedly and washed, carry out drying afterwards, obtain thermal expansivity micro-capsule 1～8.
(manufacturing of masterbatch pellet)
With powder shaped and granular low density polyethylene (LDPE) 100 weight portions with carry out mixing as two stearic amide 0.2 weight portions of the ethene of lubricant with closed mixing machine, when reaching about 140 ℃, add resulting thermal expansivity micro-capsule 50 weight portions, further mixing 30 seconds, the time system of extruding particle obtains masterbatch pellet.
(manufacturing of formed body)
Resulting masterbatch 5 weight portions are mixed with acrylic resin 100 weight portions, from the electrical ejection forming machine (JSW's corporate system, loading hopper J180AD) is supplied with resulting hybrid particles, melting mixing, carry out injection moulding, obtain tabular formed body.Above-mentioned electrical ejection forming facility have: detect one by one loading the detection machine, receive this signal and control the computer of opening of mould and mechanism mould is open with the interlock of this computer.
Molding condition is: temperature cylinder: 200 ℃, injection speed: 60mm/sec, open time delay, mold temperature for mould, and be set at the temperature shown in the table 2.
In addition, open time delay of the mould of setting in the electrical ejection forming machine and actual open time delay of mould, what produce some deviations, therefore, open time delay for mould, except setting-up time, also to write down the elapsed time, use the numerical value of elapsed time to open time delay as mould.
(comparative example 20～23)
Use CBA to replace masterbatch, CBA 5 weight portions are mixed with acrylic resin 100 weight portions, except using resulting hybrid particles, operation manufactures body similarly to Example 1.In addition, open time delay, mold temperature, be set at the time shown in the table 2, temperature for mould.
(evaluation)
Formed body for obtaining in the thermal expansivity micro-capsule that obtains in embodiment 1～8 and the comparative example 1～19 and embodiment 1～8 and the comparative example 1～23 carries out following evaluation.The results are shown in table 1～2.
(1) evaluation of thermal expansivity micro-capsule
(1-1) volume average particle size
Use size distribution footpath analyzer (LA-910, HORIBA corporate system), measure volume average particle size.
(1-2) foaming initial temperature, maximum blowing temperature, maximum displacement
Use thermo-mechanical analysis device (TMA) (TMA2940, TA instrument company system), measure foaming initial temperature (Ts), maximum displacement (Dmax) and maximum blowing temperature (Tmax).Particularly, sample 25 μ g are packed in the aluminium vessel of diameter 7mm, degree of depth 1mm, apply the power of 0.1N from above, under this state, be heated to 220 ℃ with the programming rate of 5 ℃/min from 80 ℃, the displacement on the vertical direction of measuring terminal is measured, the temperature that displacement is begun to rise is made as the foaming initial temperature, the maximum of its displacement is made as maximum displacement, the temperature in the maximum displacement is made as maximum blowing temperature.
(2) evaluation of formed body
(2-1) expansion ratio
Calculate the value that thickness of slab that thickness of slab with the formed body before the foaming removes the formed body after the foaming obtains, as expansion ratio.
(2-2) mensuration in aperture
The cross section of the foam molding that obtains is observed with two-dimentional electron reflection formula microscope (trade name " JSM-5800LV ", JEOL corporate system), with the average diameter of 50 of observed foaming as aperture (μ m).
(2-3) mensuration of proportion
The proportion of resulting formed body according to the method based on JIS K-7112A method (displacement method in the water), is measured.
(2-4) mensuration of surface roughness
For the surface state of resulting formed body, (サ one Off コ system 130A/480A (Tokyo Seimitsu Co., Ltd's system) is according to measuring maximum convex-concave based on the method for JIS B 0601 to use the surface roughness form measuring instrument.
(2-5) crazing
The visual observations crazing has or not on the surface of resulting foam molding.
(2-6) bubble state
Use the SEM device, observe the bubble state in formed body cross section with multiplying power.
As shown in Table 2, under the situation of embodiment 1～8, use has the thermal expansivity micro-capsule of the foaming initial temperature of defined scope, and mould is made as official hour open time delay, can make high foamability and apperance quality thus, form the foam molding of uniform separated foam.
On the other hand, comparative example 1～2 for use the thermal expansivity micro-capsule same with embodiment 1～2, with the situation that mould prolongs open time delay, though resulting foam molding exterior quality is good, but expansion ratio shows low value.
Comparative example 3～4 situation for using the thermal expansivity micro-capsule same, mould being shortened open time delay with embodiment 1～2, though resulting foam molding expansion ratio shows high value, but the remarkable variation of exterior quality.Comparative example 5～6 for use the thermal expansivity micro-capsule same with embodiment 5～6, with the situation that mould shortens open time delay, though exterior quality is good, expansion ratio shows low value.
In addition, the situation that foam molding is made in the combination of passing through thermal expansivity micro-capsule and mould open time delay shown in comparative example 7～19 can not satisfy expansion ratio and exterior quality simultaneously and improve.Comparative example 20～23 for using the situation of CBA, is set at 0,1,2,4 second with open time delay of mould (setting value), resulting foam molding, and appearance is poor, and the cross section foamed state also is a continuous air bubbles.
The possibility of utilizing on the industry
According to the present invention, the manufacture method of foam molding can be provided, and use this foaming and molding The manufacture method of body and the foam molding that obtains. By the method, even in injection moulding, use During the thermal expansivity micro-capsule, also carry out equably the foaming of thermal expansivity micro-capsule, can obtain thus foaming Multiplying power height and the foam molding with excellent appearance.
Claims (5)
1. foam molding, it is the foam molding that has separated foam equably, it is characterized in that, and the aperture is 60～120 μ m, and proportion is below the 0.6g/ml, and surface roughness is below the 4 μ m.
2. the manufacture method of a foam molding, it is a method of making foam molding by injection moulding, it is characterized in that,
Have: with matrix resin and foaming initial temperature is that 160～180 ℃ thermal expansivity micro-capsule is heated to the temperature more than the foaming initial temperature of described thermal expansivity micro-capsule, the melting mixing operation of preparation molten mixture; Described molten mixture is filled to back open mold in the mould, thereby makes the foamed process of described thermal expansivity micro-capsule foaming,
In described foamed process, making the time from the end-of-fill of described molten mixture to open mold is 2～4 seconds.
3. the manufacture method of a foam molding, it is a method of making foam molding by injection moulding, it is characterized in that,
Have: with matrix resin and foaming initial temperature is that 190～210 ℃ thermal expansivity micro-capsule is heated to the temperature more than the foaming initial temperature of described thermal expansivity micro-capsule, the melting mixing operation of preparation molten mixture; Described molten mixture is filled to back open mold in the mould, thereby makes the foamed process of described thermal expansivity micro-capsule foaming,
In described foamed process, making the time from the end-of-fill of described molten mixture to open mold is below 1 second.
4. according to the manufacture method of claim 2 or 3 described foam moldings, it is characterized in that the temperature that makes mould in foamed process is more than 40 ℃.
5. according to the manufacture method of claim 2,3 or 4 described foam moldings, it is characterized in that, in the melting mixing operation,, use the thermal expansivity micro-capsule of 0.5～20 weight portion with respect to matrix resin 100 weight portions.
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