JP2008127467A - Foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition that permits densification of cell nuclei, formed when a resin is impregnated with a supercritical fluid and is subjected to rapid pressure reduction from high pressure, and thereby permits micronization and densification of cells during subsequent growth of the cells, and a fine foam manufactured from the resin composition. <P>SOLUTION: The foam is formed of a composition (composition-I) comprising 100 pts.wt. of a thermoplastic resin (component A) and 0.001-30 pts.wt. of a surfactant (component B), where the foam has a length-average diameter of a cell of 0.01-1 μm and cell number density within the range of 10<SP>11</SP>-10<SP>16</SP>pieces/cm<SP>3</SP>. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is formed from a thermoplastic resin composition blended with a surfactant in order to greatly reduce the size of generated bubbles and the foaming condition dependency of the bubble density, and preferably uses a supercritical fluid as the blowing agent. The present invention relates to a produced foam having fine and high-density bubbles (hereinafter sometimes simply referred to as “fine foam”). The fine foam obtained by the present invention is lightweight and has high toughness.

  In recent years, materials having characteristics not found in conventional foams have been demanded, and miniaturization of the bubble diameter in foams has become one of the major technical problems. As a method for achieving finer and higher density of the bubble diameter, a method of impregnating a supercritical fluid into a resin and rapidly depressurizing from a high pressure is widely known. As a method for producing a foam using a supercritical fluid as a foaming agent, the following proposals have been made, for example, regarding polycarbonate resin.

  (I) A flame retardant foam obtained by foaming a flame retardant resin composition obtained by mixing a metal salt flame retardant or a polyorganosiloxane flame retardant into a polycarbonate resin with a supercritical fluid has been proposed (Patent Document 1). reference). More specifically, according to Patent Document 1, a foam formed from a resin composition in which a branched polycarbonate resin composed of bisphenol A is blended with potassium perfluorobutanesulfonate as a flame retardant is known.

  (II) A foam which is composed of a block copolymer resin of polycarbonate and polydimethylsiloxane and satisfies specific conditions is known (see Patent Document 2).

  (III) A foam formed from a resin composition in which a specific compound represented by a layered silicate organized with an organic onium ion and a styrene-maleic anhydride copolymer is blended with a polycarbonate resin is known. Yes (see Patent Document 3).

  (IV) A resin composition comprising an aromatic polycarbonate resin, an aromatic group and Si—H group-containing organosiloxane, and perfluorobutanesulfonic acid potassium salt, and a supercritical fluid as one of molding methods of the resin composition An example of foam molding using the above is shown (see Patent Document 4).

  (V) In reaction injection foam molding using a dicyclopentadiene resin, it is known that a fluorine-based surfactant and a silicone-based surfactant are effective for uniform foaming and bubble miniaturization (Patent Document 5). reference).

  However, Patent Document 1 merely discloses that a flame-retardant polycarbonate resin composition can be foam-molded, and does not sufficiently disclose a fine foam. Patent Document 2 specifically discloses a foam formed from a block copolymer resin of polycarbonate and polydimethylsiloxane and satisfying specific conditions. However, satisfactory foams were not always obtained from the specifically disclosed method. In addition, as described above, in Patent Document 1, in view of the fact that the foam produced from such a block copolymer resin under the same conditions has a large cell diameter, Patent Document 2 discloses a foam having fine bubbles and its It was difficult to fully disclose the manufacturing method.

  Although the composition of Patent Document 3 can form a fine foam, cracked foam may be generated depending on the foaming conditions to be applied, and a fine foam may not be obtained. Was sometimes required. Also, Patent Document 4 clearly shows that the resin composition of this Patent Document can be used for foam molding, but does not sufficiently disclose a fine foam. Furthermore, Patent Document 5 does not describe the relationship with the thermoplastic resin, and the cell diameter of the foam is relatively large.

Republished WO2003 / 004552 JP 2003-049018 A JP 2004-107425 A JP 2005-200526 A Japanese Patent Laid-Open No. 2003-040983

  As described above, in order to form fine bubbles, it is known that it is important to impregnate a resin with a supercritical fluid and to rapidly reduce pressure from a high pressure. At present, it is not possible to obtain sufficiently fine bubbles even if it is performed.

In view of the prior art, an object of the present invention is to increase the density of bubble nuclei generated when a resin is impregnated with a supercritical fluid and suddenly depressurized from under high pressure. An object of the present invention is to provide a resin composition that enables densification and a fine foam produced from the resin composition.

  As a result of intensive studies to achieve the above object, the present inventor has found that in a resin composition in which a thermoplastic resin typified by a polycarbonate resin is blended with a surfactant, particularly a fluorosurfactant, It was found that the diameter of the supercritical fluid impregnated becomes smaller as the pressure increases. Such an effect cannot be obtained with a single resin. The present invention has been completed by further studying from such knowledge.

According to the present invention, the subject of the present invention is (1) a composition (composition-I) containing 100 parts by weight of a thermoplastic resin (component A) and 0.001 to 30 parts by weight of a surfactant (component B). The foam has a length-average diameter of bubbles of 0.01 to 1 μm and a bubble number density of 10 ¹¹ to 10 ¹⁶ pieces / cm ^3. Achieved by the body.

  The reason why a fine foam satisfying the above condition is obtained when the pressure is reduced suddenly from high pressure by the surfactant of component B is estimated as follows. The surfactant is dispersed in a micelle form in the resin matrix, and the foaming agent is contained in the micelle by containing a foaming agent, preferably carbon dioxide (hereinafter sometimes referred to as “carbon dioxide gas”). It is thought that it can exist stably. By such stabilization, energy release at the time of pressure release is performed almost uniformly and uniformly in the entire resin matrix, and bubble nuclei are generated at high density. It is presumed that the presence of such high-density bubble nuclei makes the bubble growth due to subsequent gas inflow uniform, and fine and high-density bubbles are generated. Therefore, the action of the surfactant particularly helps the high density generation of the bubble nuclei, and thus the surfactant is a bubble nucleation aid. Moreover, it is preferable that this surfactant can make the state with a smaller micelle diameter.

  When a molded body in which bubble nuclei are generated at a high density is obtained, various methods can be selected for the subsequent bubble growth. For example, generation of bubble nuclei and bubble growth can be performed with different foaming agents. Specifically, supercritical carbon dioxide is used for the generation of bubble nuclei, and in bubble growth, the composition-I is impregnated with another inert gas such as nitrogen or argon, or in the composition-I in advance. It is possible to grow bubbles using these gases by containing a chemical foaming agent. Therefore, it can be said that carbon dioxide gas, particularly supercritical carbon dioxide gas, is suitable for the foaming agent used for high-density bubble nucleation. The foaming agent used for producing the final foam is also used as it is. Carbon dioxide is preferred because it is easy to use for bubble growth.

The upper limit of the bubble length average diameter is preferably 0.6 μm, more preferably 0.4 μm, still more preferably 0.35 μm, while the lower limit of the bubble length average diameter is preferably 0.05 μm. More preferably, it is 0.08 μm. The upper limit of the bubble density is preferably 10 ¹⁵ / cm ³ , more preferably 10 ¹⁴ / cm ³ , and the lower limit is preferably 10 ¹² / cm ³ .

  One of preferred embodiments of the present invention is: (2) The foam of the constitution (1), wherein the component A is at least one thermoplastic resin selected from a polycarbonate resin, a polyphenylene ether resin, and a polyarylate resin. Is the body.

  The resin matrix preferably has a resistance to expansion as much as possible within a range in which bubble nucleation is possible when the pressure is released. The reason is that if the resistance is large, the growth of bubble nuclei hardly occurs, and the energy of the released gas is consumed for the generation of new bubble nuclei, and as a result, the density of the bubble nuclei increases. Such resistance is affected by the viscosity and molecular weight of the resin, and the temperature when the pressure is released. Higher temperatures soften the resin and reduce resistance to expansion. The resin matrix is plasticized to some extent by impregnation with a supercritical fluid, in particular supercritical carbon dioxide. When the heat distortion temperature of the resin is too low, it becomes difficult to obtain a condition for increasing the resistance. From this point, the glass transition temperature of the component A of the present invention is preferably relatively high, specifically preferably 110 ° C. or higher, more preferably 120 ° C. or higher. Further, if the temperature is too high, the versatility is lowered, so that it is preferably 250 ° C. or lower, more preferably 200 ° C. or lower. In addition, the glass transition temperature in this invention is measured by the method prescribed | regulated to JISK7121.

  Further, the resin matrix needs to have a strength sufficient to withstand the open pressure of a high-pressure gas. From this point, the component A is at least selected from polycarbonate resins, polyphenylene ether resins, and polyarylate resins that are engineering plastics. One type of thermoplastic resin is preferred. The suitable component A can contain other thermoplastic resin in the thermoplastic resin at 50% by weight or less, preferably 30% by weight or less, more preferably 15% by weight or less. Further, when the compatibility of the other thermoplastic resins mixed with the three kinds of resins is low, the gas pressure breaks between the resin layers, and it is difficult to obtain a uniform and fine foam. Therefore, it is preferable that the three types of resins and other thermoplastic resins are sufficiently compatible, that is, the glass transition temperature of the obtained resin composition preferably has one peak.

  One of the preferred embodiments of the present invention is (3) the foam of the constitution (1) to (2), wherein the component B is a fluorine-based surfactant. As described above, it is preferable that the surfactant satisfies the conditions capable of producing a state with a small micelle diameter. For this reason, it is considered that the fluorosurfactant generates a smaller and higher density bubble diameter. Furthermore, the fluorinated organic group has an excellent affinity for supercritical carbon dioxide, which allows high-pressure carbon dioxide to be quickly and stably dispersed in the resin matrix, resulting in the formation of fine foams. It is thought to be possible. The fluorosurfactant is suitable when a supercritical fluid, particularly supercritical carbon dioxide is used as the foaming agent.

  One of the preferred embodiments of the present invention is that (4) the foam is produced by a method of impregnating a solid composition-I with a supercritical fluid of an inert gas at a pressure of 20 to 50 MPa. The foam according to any one of the features (1) to (3).

  A preferred method for producing a foam of the present invention includes a step of impregnating a gas under high pressure in the composition-I (step A), a step of reducing pressure from the high pressure to generate bubble nuclei (step B), and A step (step C) of growing such bubble nuclei into bubbles. It is well known that the production of a foam basically includes Step A to Step C. The process B and the process C may be independent processes or may be continuous processes. The independent process is generally a process for obtaining a molded body in which cell nuclei are generated as process B, and a process C as a process C by heating and softening the molded body, and using the gas contained in the molded body, The process consists of enlarging. The continuous process is a process in which final bubbles are obtained only by the decompression process, and the process B and the process C are included in the process. In this invention, it is preferable that it is an independent process from the point of the ease of bubble control. In the description of the present invention, “gas” includes supercritical fluid.

  As described above, the gas in step A is used at least for generating bubble nuclei. The gas for growing bubbles in the process C may be a gas remaining in the resin after the process B or a gas impregnated after the process B. Here, the gas to be impregnated again may be the same as or different from the gas in step A.

  Rapid pressure reduction from high pressure is important for reducing the bubble diameter and improving the bubble density in the foam. The surfactant as a bubble nucleation aid of the present invention, particularly preferably the composition-I containing a fluorosurfactant, is very suitable for a method of impregnating a gas at a higher pressure and further rapidly reducing the pressure. It is preferable to manufacture by such a method. Here, the high pressure is preferably 20 MPa or more, more preferably 23 MPa or more, and further preferably 25 MPa or more. The preferable upper limit of the high pressure varies depending on the chemical structure and molecular weight of the resin, but considering the preferred component A of the present invention, 50 MPa is preferable, 40 MPa is more preferable, and 35 MPa is still more preferable. Within this upper limit range, a certain degree of freedom in manufacturing conditions can be secured. Further, the depressurization rate in the rapid depressurization treatment is preferably 1 MPa / sec or more, more preferably 1.5 MPa / sec or more, further preferably 3 MPa / sec or more, and particularly preferably 5 MPa / sec or more. The higher the upper limit of the rate, the better. However, the practical upper limit is preferably 50 MPa / sec, more preferably 30 MPa / sec. In addition, the speed | rate of this rapid pressure reduction means the speed | rate in the range until it reaches | attains a 2 MPa lower pressure from an impregnation pressure. Further, it is preferable that the subsequent decompression speed satisfies the above range. This is because the temperature of the composition is lowered by the action of adiabatic expansion at a high pressure reduction rate, and as a result, the resistance of the matrix to the expansion of the gas can be increased.

  On the other hand, the temperature at the time of depressurization is preferably (Tg + 10−4P) ± 15 (° C.), where P (MPa) is the pressure before the depressurization treatment and Tg (° C.) is the glass transition temperature of Composition-I. It is a range. For example, when Tg is 150 ° C. and P is 25 MPa, the range is 45 to 75 ° C. The temperature is more preferably in the range of (Tg + 10-4P) ± 10 (° C.), and further preferably in the range of (Tg + 10-4P) −10 (° C.) to (Tg + 10−4P) +5 (° C.). Such a range is particularly suitable when the component A is a preferred resin as in the configuration (2). Moreover, when heating a molded object in the process C, it is preferable that the temperature of a molded object becomes the range of Tg +/- 30 (degreeC). Such a range is more preferably a range of Tg-10 (° C) to Tg + 30 (° C), and still more preferably a range of Tg (° C) to Tg + 20 (° C).

  From the above-mentioned points, a more preferable method for producing the foam of the present invention is as follows: (i) Step A, impregnating composition-I with supercritical carbon dioxide under a high pressure of 20 MPa or more, (ii) Step As B, at a temperature in the range of (Tg + 10−4P) ± 15 (° C.) with respect to Tg (° C.) of the component A, at least 1 MPa / sec or more in the range from the pressure under the high pressure to the pressure lower by 2 MPa A step of generating bubble nuclei by reducing the pressure at a reduced pressure rate, and (iii) as step C, the molded body containing the bubble nuclei obtained from step B is Tg ± 30 (° C.) with respect to Tg (° C.) of component A ), The step of growing such bubble nuclei into bubbles (step C).

  As the foaming agent used for producing the foam of the present invention, supercritical carbon dioxide gas is preferable as described above, but other than that, it is possible to use an inert gas such as nitrogen and a rare gas such as argon. it can. Further, the inert gas may be a single or a mixture of two or more, and may contain other gases at a volume fraction of 10% or less, preferably 5% or less at room temperature and atmospheric pressure. May be.

  One of the preferred embodiments of the present invention is that (5) the foam is calculated from the cut surface (observation surface) with the area ratio occupied by the bubble portion in the cut surface (observation surface) being S (%). S / Dw is the foam of said structure (1)-(4) which exists in the range of 40-500, when the length average diameter of the bubble which makes micrometer a unit is set to Dw. The index of S / Dw shows the same contents as the index in Patent Document 2, and becomes a larger value as the foam has a higher bubble density and a smaller bubble diameter. In the present invention, the lower limit of S / Dw is more preferably 60, still more preferably 70, particularly preferably 100, and the upper limit thereof is more preferably 300, still more preferably 250.

  The composition-I of the present invention preferably further contains a specific silicone compound as the C component. The silicone compound is considered to further reduce the surface tension of Composition-I and to act as a foam stabilizer for air bubbles. As a result, the silicone compound enables easier bubble nucleus generation and stable bubble growth, and as a result, a high amount of bubbles (bubble ratio) and miniaturization are compatible in the foam. When the surface tension is high, the gas energy is used for the gas flow into the already existing bubble nuclei rather than the generation of bubble nuclei that require the formation of a new surface, and the bubble density is less likely to increase.

  Here, the specific silicone compound means that (I) the ratio of containing aromatic groups (the amount of aromatic groups) is 10 to 70% by weight and / or (II) the ratio of containing Si-H groups is 0. .1 to 1.66 mol / 100 g of a silicone compound. As described above, the composition-I of the present invention preferably has a strength sufficient to withstand the open pressure of a high-pressure gas, and it is not preferable that the compatibility with the component A is inferior. When the compatibility is poor, the foaming gas does not expand the whole uniformly, but explosively destroys the inside and leads to crack-like foaming.

  On the other hand, in the silicone compound of component C, such cracked foaming is suppressed. Although the reason for this is not clear, it is conceivable that having a specific amount of aromatic group improves the compatibility with the suitable A component typified by polycarbonate resin. In addition, when having a specific Si-H group amount, at the time of preparation of Composition-I, there is a considerable binding reaction between silicone compounds or resin components, resulting in an increase in molecular weight and a bond with the resin. Phase separation is expected to be suppressed. On the other hand, since the Si—H group itself has a good affinity with a gas, particularly its supercritical fluid, due to its non-polarity, it is considered that it has an effect of further stabilizing the generation of bubble nuclei and subsequent growth.

Details of the present invention will be described below.
<About component A>
Examples of the component A thermoplastic resin of the present invention include polyolefin resin, polyester resin, polystyrene resin, acrylic resin, polyamide resin, polyalkylene ether resin, polyurethane resin, polycarbonate resin, polyphenylene ether resin, polyarylate resin, polyphenylene sulfide. Examples include resins, polysulfone resins, polyether sulfone resins, cyclic polyolefin resins, polyetherimide resins, polyamideimide resins, polyimide resins, and polyaminobismaleimide resins. Any of the above-mentioned resins may be a copolymer composed of a plurality of structural units, and the copolymer forms thereof are random copolymers, graft copolymers, block copolymers, and higher order structures. It may be a controlled copolymer structure. Copolymer resins of vinyl monomers typified by styrene are widely used and can be used as the component A in the present invention. For example, AS resin (resin mainly composed of acrylonitrile-styrene copolymer), SMA resin (resin mainly composed of styrene-maleic anhydride copolymer), MS resin (resin mainly composed of methyl methacrylate-styrene copolymer) and Examples thereof include ABS resin (resin mainly composed of acrylonitrile-styrene-butadiene copolymer).

  In order to produce finer and more uniform foaming in the bubble nucleation in Step B, it is preferable that the number of crystals in the resin is small, and from this point, the A component is preferably an amorphous thermoplastic resin. The A component of the present invention has a Tg of preferably 110 ° C. or higher, more preferably 120 ° C. or higher. Such Tg is preferably 250 ° C. or lower, more preferably 200 ° C. or lower. Hereinafter, a more preferable A component will be described.

<Polycarbonate resin>
The polycarbonate resin which is the component A (hereinafter sometimes simply referred to as “polycarbonate”) is known per se and has been used for various molded products. That is, it is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  The polycarbonate resin may be various polycarbonate resins having a low crystallinity, a high heat resistance, or a low water absorption rate, which are polymerized using other dihydric phenols, in addition to the commonly used bisphenol A type polycarbonate. . The polycarbonate resin may be produced by any production method, and in the case of interfacial polycondensation, a terminal stopper of a monohydric phenol is usually used. The polycarbonate resin may also be a branched polycarbonate resin obtained by polymerizing trifunctional phenols, and further a copolymer obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a divalent aliphatic or alicyclic alcohol. Polycarbonate may be used.

  In the present invention, bisphenol A type polycarbonate resin is more preferable in the following points. The polycarbonate resin according to the first aspect is particularly excellent in impact resistance and can suitably exhibit the advantages of the fine foam. That is, fine bubbles in the fine foam can impart higher toughness to the foam, as in the case of containing a rubber granule as a starting point for craze formation. This makes it possible to provide a molded article that is excellent in impact resistance and tensile elongation and is lightweight. Secondly, the polycarbonate resin is relatively easy to crystallize, and as a result, it takes a hardening behavior such as crystallization by an inert gas, particularly supercritical carbon dioxide, and as a result, foaming tends to be uneven or non-foaming.

（Ａは下記式（ｉ−１）〜（ｉ−３）および（ｉ−５）からなる群より選択される少なくとも１種の二価の有機残基、単結合、または下記式（ｉ−４）のいずれかの結合を表し、ｓおよびｔはそれぞれ独立して０または１〜４の整数であり、Ｒ_１３およびＲ_１４はそれぞれ独立して、ハロゲン原子、または炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２０のシクロアルキル基、炭素数６〜２０のシクロアルコキシ基、炭素数６〜１０のアリール基、炭素数７〜２０のアラルキル基、炭素数６〜１０のアリールオキシ基、および炭素数７〜２０のアラルキルオキシ基からなる群より選択される有機残基を表す。） A suitable structural unit of the polycarbonate of the present invention is represented by the following formula (i).

(A is at least one divalent organic residue selected from the group consisting of the following formulas (i-1) to (i-3) and (i-5), a single bond, or the following formula (i-4 ) And s and t are each independently 0 or an integer of 1 to 4, and R ₁₃ and R ₁₄ are each independently a halogen atom or an alkyl group having 1 to 10 carbon atoms. , An alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and a carbon number It represents an organic residue selected from the group consisting of an aryloxy group having 6 to 10 carbon atoms and an aralkyloxy group having 7 to 20 carbon atoms.)

（式（ｉ−１）中、Ｒ_１５、Ｒ_１６、Ｒ_１７およびＲ_１８はそれぞれ独立して、水素原子、ハロゲン原子または炭素数１〜３のアルキル基を表す。）

(In formula (i-1), R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 3 carbon atoms.)

（式（ｉ−２）中、Ｒ_１９およびＲ_２０はそれぞれ独立して、水素原子、ハロゲン原子または炭素数１〜３のアルキル基を表す。）

(In formula (i-2), R ₁₉ and R ₂₀ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms.)

（上記式（ｉ−３）において、ｕは４〜１１の整数を表し、かかる複数のＲ_２１およびＲ_２２はそれぞれ独立して水素原子、ハロゲン原子、および炭素数１〜３のアルキル基から選択される基を表す。）

(In the above formula (i-3), u represents an integer of 4 to 11, and the plurality of R ₂₁ and R ₂₂ are each independently selected from a hydrogen atom, a halogen atom, and an alkyl group having 1 to 3 carbon atoms. Represents a group to be

（式（ｉ−５）中、Ｒ_２３およびＲ_２４はそれぞれ独立して、水素原子、ハロゲン原子、および炭素数１〜１０の炭化水素基から選択される基を表す。）

(In formula (i-5), R ₂₃ and R ₂₄ each independently represent a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group having 1 to 10 carbon atoms.)

Next, specific examples of the formula (i) will be described based on specific examples of the dihydroxy compound from which the structural unit is derived.
Examples of the compound when A in Formula (i) is a single bond include 4,4′-biphenol and 3,3 ′, 5,5′-tetrafluoro-4,4′-biphenol.

  Examples of the compound when A is the formula (i-1) include α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropyl. Benzene (usually referred to as “bisphenol M”), α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, and α, α′-bis (4-hydroxyphenyl) -m-bis (1 , 1,1,3,3,3-hexafluoroisopropyl) benzene.

  As the compound when A is the formula (i-2), 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9- Bis (3-fluoro-4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-3-trifluoromethylphenyl) fluorene.

  As the compound when A is the formula (i-3), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1, Examples include 1-bis (3-fluoro-4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) perfluorocyclohexane.

  As the compound when A is any one of the formulas (i-4), 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 4, 4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4, 4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-diphenyl sulfide, 4,4'-dihydroxy-3,3'-diphenyl sulfoxide, and 4,4 And '-dihydroxy-3,3'-diphenylsulfone.

  As the compound when A is any one of the formula (i-5), 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (usually referred to as “bisphenol A”), 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) ) Propane (usually referred to as “bisphenol C”), 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxy-3) -Phenylphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) Lopan, 2,2-bis (4-hydroxyphenyl) butane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxy) Phenyl) decane, 1,1-bis (3-methyl-4-hydroxyphenyl) decane, 1,1-bis (2,3-dimethyl-4-hydroxyphenyl) decane, 2,2-bis (3-bromo-4) -Hydroxyphenyl) propane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 2,2-bis (4-hydroxyphenyl) -1,1,1, 3,3,3-hexafluoropropane (usually referred to as “bisphenol AF”), 2,2-bis (4-hydroxy-3-methyl) Phenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane, 2,2-bis (3-fluoro-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, and 2,2-bis (3,5-difluoro-4- Hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4) -Hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane.

  Among them, bisphenol M in formula (i-1), 9,9-bis (4-hydroxy-3-methylphenyl) fluorene in formula (i-2), 1,1-bis in formula (i-3) (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 3,3′-dimethyl-4,4′-dihydroxydiphenyl in formula (i-4) In the sulfide and formula (i-5), bisphenol A, bisphenol C, bisphenol AF, and 1,1-bis (4-hydroxyphenyl) decane are preferred.

  As for other details of the polycarbonate resin of the present invention, for example, WO03 / 080728 pamphlet, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. Etc. are described.

  As the polycarbonate resin of component A of the present invention, not only virgin raw materials but also polycarbonate resins regenerated from used products, so-called material-recycled polycarbonate resins can be used. Used products include soundproof walls, glass windows, translucent roofing materials, various glazing materials represented by automobile sunroofs, transparent members such as windshields and automobile headlamp lenses, containers such as water bottles, and optical recording media Etc. are preferable. These do not contain a large amount of additives or other resins, and the desired quality is easily obtained stably. In particular, an automobile headlamp lens, an optical recording medium, and the like are preferred as preferred embodiments because they satisfy the more preferable conditions of the viscosity average molecular weight. The virgin raw material is a raw material not yet used in the market after its production.

The viscosity average molecular weight of the polycarbonate resin of component A is preferably in the range of 1.5 × 10 ^{4 to} 5.0 × 10 ⁴ . When the viscosity average molecular weight of the polycarbonate is less than 1.5 × 10 ⁴ , it may be difficult to control foaming, and toughness such as impact strength and elongation tends to be lowered. On the other hand, if it exceeds 5.0 × 10 ⁴ , melt processing tends to be difficult, which is not preferable in the present invention. The lower limit of the viscosity average molecular weight is more preferably 2.2 × 10 ⁴ , still more preferably 2.4 × 10 ⁴ . The upper limit of the viscosity average molecular weight is more preferably 4.5 × 10 ⁴ , still more preferably 4.0 × 10 ⁴ . The polycarbonate having a viscosity average molecular weight in the above preferred range is excellent in balance of processability, strength, finer bubble diameter, and uniform bubble diameter.

The viscosity average molecular weight may be satisfied as the whole component A, and includes those satisfying such a range by a mixture of two or more kinds having different molecular weights. In particular, the mixing of polycarbonate having a viscosity average molecular weight of 5.0 × 10 ⁴ , more preferably 8.0 × 10 ⁴ or more, and still more preferably 10.0 × 10 ⁴ or more increases entropy elasticity at the time of melting and foams. The conditions at the time of body manufacture are expanded, and a good foam can be obtained more easily. Therefore, mixing polycarbonate with a viscosity average molecular weight exceeding 5.0 × 10 ⁴ is one of the preferred choices when such improvements are required. This effect becomes more prominent as the molecular weight of the polycarbonate is higher, but the upper limit of the molecular weight is practically 200 × 10 ⁴ , preferably 30 × 10 ⁴ , more preferably 20 × 10 ⁴ . It is preferable that the high molecular weight component is mixed in such an amount that the molecular weight distribution of two or more peaks can be observed in a measuring method such as GPC (gel permeation chromatography).

In the polycarbonate resin (component A) of the present invention, the phenolic hydroxyl group content is preferably 30 eq / ton or less, more preferably 25 eq / ton or less, and further preferably 20 eq / ton or less. Such a value can be substantially 0 eq / ton by sufficiently reacting the terminal terminator. The amount of the phenolic hydroxyl group is determined by performing ¹ H-NMR measurement, and calculating the molar ratio of the dihydric phenol unit having a carbonate bond, the divalent phenol unit having a phenolic hydroxyl group, and the terminal terminator unit. It is calculated | required by converting into the amount of phenolic hydroxyl groups per polymer weight based.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of polycarbonate at 20 ° C. in 100 ml of methylene chloride, the specific viscosity calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The obtained specific viscosity is inserted by the following equation to determine the viscosity average molecular weight M.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

<Polyphenylene ether resin>
The polyphenylene ether resin used in the present invention is a polymer or copolymer of a nucleus-substituted phenol having a phenylene ether structure (hereinafter sometimes simply referred to as a PPE polymer), and if necessary, a styrene polymer, It contains a rubber-modified styrenic polymer. Examples of the nuclear substituent include a hydrocarbon group having 1 to 5 carbon atoms which may have a halogen atom or an oxygen atom, and the number thereof is 1 to 4, preferably 2 to 3.

  Typical examples of the polymer of the nucleus-substituted phenol having a phenylene ether structure include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-1,4-phenylene) ether. Poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1) , 4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl) -6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, and the like. Of these, poly (2,6-dimethyl-1,4-phenylene) ether is particularly preferred.

  Representative examples of the copolymer of a nucleus-substituted phenol having a phenylene ether structure include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6-dimethylphenol and o-cresol, Or a copolymer of 2,6-dimethylphenol with 2,3,6-trimethylphenol and o-cresol.

  The method for producing the above PPE polymer is not particularly limited. For example, according to the method described in US Pat. No. 4,788,277 (Japanese Patent Application No. 62-77570), in the presence of dibutylamine. In addition, 2,6-xylenol can be produced by oxidative coupling polymerization.

  Various molecular weights and molecular weight distributions of polyphenylene ether resins can be used. The molecular weight is 0.5 g / dl chloroform solution, and the reduced viscosity at 30 ° C. is 0.20 to 0.70 dl / g. The range is preferable, and the range of 0.30 to 0.55 dl / g is more preferable.

  In addition, in the polyphenylene ether resin of the present invention, other various phenylene ether units that have been proposed to exist in the polyphenylene ether resin as long as they do not contradict the gist of the present invention are partially structured. May be included. Examples of those proposed to coexist in a small amount include 2- (dialkylaminomethyl) -6-methylphenylene ether described in Japanese Patent Application Nos. 63-12698 and 63-301222. Unit, 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit, and the like. Also included are those in which a small amount of diphenoquinone or the like is bonded to the main chain of the polyphenylene ether resin.

  As the polyphenylene ether resin of the present invention, those containing a styrene polymer and a rubber-modified styrene polymer can also be used. The ratio of the styrene polymer and / or the rubber-modified styrene polymer (hereinafter sometimes referred to simply as PS polymer) and the PPE polymer is such that the PPE polymer is at least 20 in 100% by weight of the total. It is necessary to be at least wt%. The PPE polymer is more preferably 30% by weight or more. The flame retardancy is more preferable as the proportion of the PPE polymer is increased, but it may be inferior in molding processability. Therefore, the PPE polymer is more preferably in the range of 30 to 80% by weight.

  As the vinyl aromatic compound polymer, in addition to styrene, o-methyl styrene, p-methyl styrene, m-methyl styrene, 2,4-dimethyl styrene, ethyl styrene, p-tert-butyl styrene, and other nuclear alkyl-substituted styrenes , Polymers such as α-alkyl-substituted styrene such as α-methylstyrene and α-methyl-p-methylstyrene, and copolymers of one or more of these with at least one of other vinyl compounds, these two The above copolymer is mentioned.

  Examples of the compound copolymerizable with the vinyl aromatic compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, and acid anhydrides such as maleic anhydride. . Among these polymers, particularly preferred are polystyrene (including syndiotactic polystyrene) and styrene-acrylonitrile copolymer (AS resin).

  Examples of the rubber used in the rubber-modified vinyl aromatic compound polymer include polybutadiene, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, natural rubber, and ethylene-propylene copolymer. . In particular, polybutadiene and styrene-butadiene copolymer are preferable, and rubber-modified aromatic compound polymer is preferably rubber-modified polystyrene (HIPS) and rubber-modified styrene-acrylonitrile copolymer (ABS resin).

  Further, the polyphenylene ether resin may also include a polyphenylene ether resin modified with an ethylenically unsaturated compound such as the following α, β-unsaturated carboxylic acid or anhydride thereof. When a polyphenylene ether-based resin modified using these is used, it is possible to provide a molded article having excellent mixing properties with a vinyl compound-based polymer and free from phase separation. Examples of α, β-unsaturated carboxylic acids or anhydrides thereof include maleic anhydride, phthalic acid, itaconic anhydride, and glutaconic anhydride described in JP-B-49-2343 and JP-B-3-52486. Citraconic anhydride, aconitic anhydride, hymic anhydride, 5-norbornene-2-methyl-2-carboxylic acid, or maleic acid, fumaric acid, etc., but are not limited thereto, maleic anhydride Is particularly preferred.

  Reaction of α, β-unsaturated carboxylic acid such as maleic anhydride or its anhydride with polyphenylene ether resin is carried out by mixing both in the presence or absence of organic peroxide, and the glass transition of PPE polymer. It can manufacture by heating to the temperature more than temperature. When producing the flame retardant resin composition of the present invention, a polyphenylene ether-based resin in which an α, β-unsaturated carboxylic acid such as maleic anhydride or an anhydride thereof is bonded in advance may be used. Moreover, when manufacturing a flame-retardant resin composition, the method of making it react with a polyphenylene ether polymer by adding (alpha), (beta)-unsaturated carboxylic acid, such as maleic anhydride, or its anhydride may be sufficient.

<Polyarylate resin>
The polyarylate resin of the present invention is obtained from an aromatic dicarboxylic acid or a derivative thereof and a dihydric phenol or a derivative thereof. The aromatic dicarboxylic acid used for the preparation of the polyarylate may be any one as long as it reacts with a dihydric phenol to give a satisfactory polymer, and is used alone or in combination of two or more.
Preferred aromatic dicarboxylic acid components include terephthalic acid and isophthalic acid. A mixture thereof may also be used.

  Specific examples of the dihydric phenol component include 2,2-bis (4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4 , 4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenylmethane, 2,2′-bis (4hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1, Examples include 1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl, hydroquinone, and the like. These dihydric phenol components are para-substituted products, but other isomers may be used, and ethylene glycol, propylene glycol, neopentyl glycol and the like may be used in combination with the dihydric phenol component.

  Among these, preferred polyarylate resins include those in which the aromatic dicarboxylic acid component is composed of terephthalic acid and isophthalic acid, and the divalent phenol component is composed of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). It is done. The ratio of terephthalic acid to isophthalic acid is preferably terephthalic acid / isophthalic acid = 9/1 to 9/1 (molar ratio), particularly preferably 7/3 to 3/7 in terms of melt processability and performance balance.

Other typical polyarylate resins include those in which the aromatic dicarboxylic acid component is composed of terephthalic acid and the dihydric phenol component is composed of bisphenol A and hydroquinone. The ratio of bisphenol A and hydroquinone is preferably bisphenol A / hydroquinone = 50/50 to 70/30 (molar ratio), more preferably 55/45 to 70/30, and still more preferably 60/40 to 70/30. .
The viscosity average molecular weight of the polyarylate resin in the present invention is preferably in the range of about 7,000 to 100,000 in view of physical properties and extrusion processability. The polyarylate resin can be selected from any polymerization method of interfacial polycondensation and transesterification.

<About B component>
The B component surfactant changes the interfacial energy in the dilute solution. Structurally, a hydrophilic group that is polar and dissolves in water or exhibits affinity, and a lipophilic group that is less polar than nonpolar or hydrophilic groups and dissolves in an organic solvent or exhibits affinity A compound having both a group and a hydrophobic group can be used.
As the surfactant, any of a cationic compound, an anionic compound, and a nonionic compound can be used as classified by hydrophilic group. Further, a surfactant in which a cationic active site, an anionic active site, and a nonionic active site such as polyalkylene oxides are combined may be used.

  Preferred examples of the cationic compound used as the component B include quaternary ammonium salts and quaternary phosphonium salts. Such a quaternary ammonium salt may be any of an aliphatic ammonium salt, an aromatic ammonium salt, and a heterocyclic ammonium salt, and the same applies to a phosphonium salt. Examples of the heterocyclic ammonium salt include pyridinium salts and imidazolinium salts.

  As the anionic compound of component B, carboxylate, sulfonate, sulfate ester, phosphate ester and the like are preferably exemplified. Among them, sulfonate and phosphorus are preferable from the viewpoint of the thermal stability of Composition-I. Acid esters are preferred. The anionic compound of component B may be a polymer compound having a repeating unit substituted with a group consisting of a salt which is an active site thereof. Specific examples of the polymer serving as the base of the polymer type anionic compound include, for example, polyether ester, polyester, polyurethane, polystyrene and styrene copolymer, and polycarbonate. Preferable examples of the counter ion of the B component anionic compound include alkali metal ions, alkaline earth metal ions, zinc ions, and organic onium ions such as organic phosphonium ions and organic ammonium ions.

  The nonionic compound which is one embodiment of the B component of the present invention is a compound having, as a hydrophilic group, an OH group (hydroxyl group) or an ether bond (—O—) that is not ionically dissociated in water. There is a polyhydric alcohol type. Polyalkylene oxide types include polyalkylene oxide adducts of higher alcohols, polyalkylene oxide adducts of alkylphenols, polyalkylene oxide adducts of fatty acids, polyalkylene oxide adducts of polyhydric alcohol fatty acid esters, and polyalkylenes of fats and oils. Examples include oxide adducts. Examples of the polyhydric alcohol type include fatty acid esters of polyhydric alcohols such as glycerin, pentaerythritol, and sorbitol.

  Examples of the lipophilic group of the component B of the present invention include an alkyl group, an alkylaryl group, and a naphthalene group in a low molecular compound, and in a polymer compound, ethylene, propylene, styrene, α-methylstyrene, In addition, structural units derived from ethylenically unsaturated monomers represented by various acrylates and methacrylates are exemplified. As the oleophilic acrylate and methacrylate (hereinafter referred to as “(meth) acrylate”), methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2- Examples include ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and phenyl (meth) acrylate.

  On the other hand, preferred examples of the hydrophobic group include fluorinated organic moieties such as siloxane units and fluoroalkyl groups. As the component B of the present invention, a silicone surfactant containing such a siloxane unit and a fluorine surfactant containing a fluorinated organic moiety are preferable, and a fluorine surfactant is particularly preferable. Such surfactants, particularly fluorine-based surfactants, have a high non-polarity of such hydrophobic groups and are excellent in affinity with supercritical carbon dioxide gas, and as a result, it is possible to mold finer foams.

  The fluorosurfactant of the present invention contains a hydrophobic group composed of a hydrophilic group and a fluorinated organic moiety. The surfactant is a polymer comprising a homopolymer of a fluorine-containing organic group-containing ethylenically unsaturated monomer, or a copolymer of the monomer and a monomer copolymerizable with the monomer. All of the compounds and other low molecular weight compounds are included, and any of nonionic, anionic, cationic, and amphoteric systems are included. It may have a combination of a nonionic system and another system.

  As the low molecular weight compound fluorine-containing surfactant, cationic and nonionic surfactants are particularly preferable, and compounds represented by the following general formulas (ii-1) to (ii-4) are particularly preferable. is there.

Where Rf is a C 1-20 perfluoro group or partially fluorinated alkyl group, X and Y are single bonds or divalent organic groups, and M is an alkali metal, alkaline earth metal, zinc, organic It represents phosphonium, organic ammonium, —NH ₄ , a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. However, in the case of a divalent metal ion, 1 mol of metal ion corresponds to 2 mol of anion portion. j is an integer of 1, 2 or 3, and A represents an alkylene oxide group or an alkylene oxide repeating group having a polymerization degree of 50, preferably up to 30, and R ′ is a hydrogen atom or a carbon number of 1 to 3. 20 hydrocarbon groups are represented.

Preferable specific examples of the divalent organic group represented by X in formulas (ii-1) to (ii-3) include —SO ₂ N (CH ₃ ) CH ₂ —, —SO ₂ N (C _{3 H 7) CH 2 -, -} SO 2 NHCH 2 CH 2 OCOCH 2 CH 2 -, - SO 2 NHCH 2 CH 2 CH 2 -, - SO 2 N (C 3 H 7) CH 2 CH 2 -, - CH 2 _{CH 2 -, - CH 2 CH} 2 OCOCH 2 CH 2 -, - SO 2 N (C 3 H 7) -A-COCH 2 CH 2 -, and -A-COCH ₂ CH ₂ - and the like. In the latter two groups, A is the same as in the case of formula (ii-4). Specific examples of suitable divalent organic groups for Y in formula (ii-4) include —SO ₂ N (C ₃ H ₇ ) — and —SO ₂ NH—.

More preferred X is a single bond, —CH ₂ CH ₂ —, and —CH ₂ CH ₂ OCOCH ₂ CH ₂ —, and more preferred Y is a single bond, and —SO ₂ N (C ₃ H ₇ ). -. When A is an alkylene oxide repeating group, the repeating group may contain a plurality of alkylene oxide groups. Further, R ′ is preferably a hydrogen atom. Also in the fluorosurfactant, sulfonates and phosphate esters are preferable, and among them, the compounds of the above formulas (ii-1) and (ii-3) are preferable as the component B, and sulfonates are particularly preferable. The compound of ii-1) is preferable.

  Examples of the fluorine-based surfactant of the polymer compound include a homopolymer of a fluorine-containing organic group-containing ethylenically unsaturated monomer, or a copolymer of the monomer and a monomer copolymerizable with the monomer. A polymer is mentioned. As the fluorine-containing organic group in such a monomer, a perfluoroalkyl group is preferable. As the perfluoroalkyl group-containing ethylenically unsaturated monomer, a compound represented by the following general formula (iii) is preferably exemplified.

In the formula (iii), R _f represents a linear, branched, or perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group containing a carbon atom in the main chain, and R ₁ is -H (hydrogen atom), - CH ₃ (methyl group), - Cl, -F, and _{-CH 2 CH 2 C m F 2m} + 1 ( where m is an integer from 1 to 20) represent, Z is a single Represents a bond or a divalent organic group.

Specific examples of the divalent organic group for Z in the formula (iii) include the following groups. Wherein n represents an integer of 1 to 10 in the formula, _{R 2} is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Specific examples of R _f in the formula (iii) include the following groups. However, p and r in a following formula represent the integer of 1-20, q represents the integer of 0 or 1-17.

Furthermore, as a specific example of the formula (iii),
_{CH 2 = C (CH 3)} COOCH 2 CH 2 (CF 2) n CF 3 ( where n is the average value at 5 to 11 to about 9),
_{CH 2 = C (CH 3)} COOCH 2 CH 2 C 8 F 17,
_{CH 2 = C (CH 3)} COOCH 2 CH 2 (CF 2) 5 CF 3,
_{CH 2 = CHCOO (CH 2)} 3 (CF 2) 6 CF (CF 3) 2,
_{CH 2 = CHCOO (CH 2)} 3 (CF 2) 10 CF (CF 3) 2
_{CH 2 = C (CH 3)} COOCH 2 CH 2 N (C 3 H 7) SO 2 (CF 2) 5 CF 3,
_{CH 2 = CHCOOCH 2 CH 2 N} (C 3 H 7) SO 2 (CF 2) 7 CF 3,
_{CH 2 = C (CH 3)} COOCH 2 CH 2 N (CH 3) SO 2 (CF 2) 7 CF 3,
_{CH 2 = CHCOOCH 2 CH 2 N} (CH 3) SO 2 (CF 2) 7 CF 3,
_{CH 2 = CHCOO (CH 2)} 4 (CF 2) 7 CF 3,
_{CH 2 = CHCOO (CF 2)} 6 CF 3,
_{CH 2 = CHCOO (CH 2)} 4 N (C 4 H 9) SO 2 (CF 2) 7 CF 3,
_{CH 2 = CHCOOCH 2 CH (OH} ) CH 2 (CF 2) 7 CF 3,
_{CH 2 = C (CH 3)} COOCH 2 CH 2 N (C 3 H 7) CO (CF 2) 7 CF 3, and _{CH 2 = CHCOOCH 2 CH 2 N} (C 2 H 5) CO (CF 2) 7 CF ₃ etc. can be illustrated suitably. Among them, CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ C ₈ F ₁₇ is preferable. Details of specific examples of the formula (iii) containing such compounds are described as formulas “a-1” to “a-56” in JP-A No. 11-209787.

  Monomers that can be copolymerized with a fluorine organic group-containing ethylenically unsaturated monomer include, for example, ethylene, propylene, vinyl chloride, vinylidene chloride, styrene, α-methylstyrene, vinyl acetate, methyl (meth) acrylate, and ethyl. (Meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl vinyl ether, Propyl vinyl ether, octyl vinyl ether, butadiene, isoprene, chloroprene, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, (meth) acrylamide, N-methylol (meth) acrylamide, 3-chloro-2-hydroxy (meth) ) Acrylate and diacetone acrylamide, and compounds represented by the following general formula (iv) are exemplified.

  The component B composed of the polymer compound of the present invention, particularly the fluorosurfactant of the polymer compound, can contain a structural unit derived from a silicone chain-containing ethylenically unsaturated monomer.

As the silicone chain-containing ethylenically unsaturated monomer, a compound represented by the following general formula (iv) is preferably exemplified.

In the formula (iv), R ₁ represents —H, —Cl, —F, —CH ₃ , and R ₂ and R ₃ are each represented by an alkyl group having 1 to 20 carbon atoms, a phenyl group, or the following formula: R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each represents an alkyl group having 1 to 20 carbon atoms or a phenyl group, and X represents —CH ₂ CH (OH) CH ₂ OCO—. , — (CH ₂ ) _n NHCH ₂ CH (OH) CH ₂ OCO—, — (CH ₂ ) _n OCO—, — (CH ₂ ) _n —O— (CH ₂ ) _m —OCO—, —OCH ₂ CH ( OH) CH ₂ OCO—, or — (CH ₂ ) _n —C (CF ₃ ) ₂ OCO—, q represents 0 or an integer of 1 to 500, and p represents 0 or 1, M and n in the formula each represents an integer of 2 to 6 .

前記式（ｖ）において、Ｒ_９、Ｒ_１０、Ｒ_１１、Ｒ_１２およびＲ_１３は、それぞれ炭素数１〜２０のアルキル基もしくはフェニル基を表し、ｒは０もしくは１〜３の整数を表す。

In the formula (v), R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ each represent an alkyl group having 1 to 20 carbon atoms or a phenyl group, and r represents an integer of 0 or 1 to 3.

  The details of the specific example of the formula (iv) are described in Japanese Patent Application Laid-Open No. 11-209787, the formulas “b-1-1” to “b-1-36”, “b-2-1” to “b-2-7”. ", And" b-3-1 "to" b-3-9 ".

Furthermore, as a more preferable aspect of the said formula (iv), following (vi-1)-(vi-3) is mentioned.

  In the formulas (vi-1) to (vi-3), p represents 0 or an integer of 1 to 500, p ′ represents 0 or a positive integer whose sum with p ″ is 1 to 500, and p ″. Represents an integer of 1 to 500, and r, s, and t represent 0 or an integer of 1 to 3, and the three may be the same or different. The upper limit of p is preferably 60, more preferably 10, and still more preferably 8. Further, in the formulas (vi-1) to (vi-3), more preferred are the formulas (vi-1) and (vi-3). Among them, a monomer having a molecular weight of the silicone chain of preferably 5,000 or less, more preferably 100 to 1,000 is preferable, particularly a monomer represented by the formula (vi-3), among which r, s and t are In any case, a monomer of 0 is particularly preferable.

  The B component comprising the polymer compound of the present invention, particularly the fluorosurfactant of the polymer compound, can contain a structural unit derived from a polyalkylene oxide group-containing ethylenically unsaturated monomer. As the monomer, it is preferable to use mono (meth) acrylic acid ester of poly (alkylene oxide) glycol such as polyethylene glycol, polypropylene glycol, and a copolymer of ethylene oxide and propylene oxide. The terminal of such poly (alkylene oxide) glycol can be capped with an alkyl group having 1 to 6 carbon atoms. The degree of polymerization of such poly (alkylene oxide) units is preferably from 1 to 100. More preferable embodiments of such a monomer are a mono (meth) acrylate ester of a copolymer of ethylene oxide and propylene oxide, and a di (meth) acrylate ester of polyethylene glycol.

  In the fluorosurfactant of the polymer compound, the composition ratio of the structural unit derived from the perfluoroalkyl group-containing ethylenically unsaturated monomer is 5 to 95% by weight, preferably 10 to 70% by weight, more preferably Is 15 to 65% by weight. In the fluorosurfactant of the polymer compound, the upper limit of the composition ratio of the structural unit derived from the silicone chain-containing ethylenically unsaturated monomer is 60% by weight, preferably 40% by weight, more preferably 20% by weight. is there. In the fluorosurfactant of the polymer compound, the upper limit of the composition ratio of the structural unit derived from the polyalkylene oxide group-containing ethylenically unsaturated monomer is 60% by weight, preferably 40% by weight, more preferably 20% by weight. %. Furthermore, in the fluorosurfactant of the polymer compound, the composition ratio of structural units derived from other ethylenically unsaturated monomers is 5 to 95% by weight, preferably 30 to 90% by weight, more preferably 35 to 85% by weight.

The molecular weight of the polymer compound of the present invention is preferably in the range of 500 to 10,000, more preferably in the range of 600 to 9,000, and more preferably in the range of 700 to 8,800. A range of 000 is more preferred.
The composition ratio of component B is 0.001 to 30 parts by weight based on 100 parts by weight of component A, preferably 0.01 to 10 parts by weight, more preferably 0.05 to 1 part by weight, still more preferably. 0.05 to 0.3 parts by weight. Within the above range, a fine foam having more excellent mechanical properties can be obtained.

<About component C>
In the present invention, as described above, a silicone compound that satisfies the following conditions (I) and / or (II) is preferably contained as the C component. (I) The ratio (aromatic group amount) containing aromatic groups is 10 to 70% by weight, and / or (II) the ratio containing Si-H groups is 0.1 to 1.66 mol / 100 g. is there. The effect of the specific amount of the specific group is as described above. More preferably, the component C is (III) a silicone compound having an average degree of polymerization of 3 to 150. Here, the degree of polymerization is [(R) _a SiO _{(4-a) / 2} ] (where R represents an atom bonded to a Si atom or a monovalent group, and a is an integer of 0 or 1 to 3). Represents the degree of polymerization.

  Further, M is a monofunctional siloxane unit (a = 3 in the above formula), D is a bifunctional siloxane unit (a = 2 in the above formula), and T is a trifunctional siloxane unit (a = 1 in the above formula). ) Is more preferably a silicone compound comprising MD units or MDT units. That is, a silicone compound consisting only of M units and D units, or a silicone compound consisting only of M units, D units and T units is suitable as the B component. Here, the functionality means the number of bonds for the siloxane bond that one siloxane unit has.

  The aromatic group of component C is preferably an aromatic group represented by the following general formula (vii). Among them, a phenyl group is most preferable (that is, n = 0 in the following formula (vii)).

（式（ｖｉｉ）中、ＸはＯＨ基または炭素数１〜２０の一価の炭化水素基を示す。ｎは０〜５の整数を表わす。さらに式（ｖｉｉ）中においてｎが２以上の場合はｎ個のＸはそれぞれ独立に上記群から選択することができる。）

(In the formula (vii), X represents an OH group or a monovalent hydrocarbon group having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in the formula (vii), when n is 2 or more. N can be independently selected from the above group.)

  A more preferable component C satisfies the conditions (I) and / or (II), preferably (III), and includes at least one selected from structural units represented by the following general formulas (viii) and (ix) It is a silicone compound containing.

（式（ｖｉｉｉ）および式（ｉｘ）中、Ｚ^１〜Ｚ^３はそれぞれ独立に水素原子、炭素数１〜２０の一価の炭化水素基、または下記一般式（ｘ）で示される化合物を示す。α^１〜α^３はそれぞれ独立に０または１を表わす。ｍ^１は１以上の整数を表わす。さらに式（ｖｉｉｉ）中においてｍ^１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (viii) and formula (ix), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a compound represented by the following general formula (x) Α ^{1 to} α ³ each independently represents 0 or 1. m ¹ represents an integer of 1 or more, and in formula (viii), when m ¹ is 2 or more, the repeating unit is a plurality of repeating units different from each other. Can take units.)

（式（ｘ）中、Ｚ^４〜Ｚ^８はそれぞれ独立に水素原子、炭素数１〜２０の一価の炭化水素基を示す。α^４〜α^８はそれぞれ独立に０または１を表わす。ｍ^２は０もしくは１以上の整数を表わす。さらに式（ｘ）中においてｍ^２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (x), Z ^{4 to} Z ⁸ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Α ^{4 to} α ⁸ each independently represents 0 or 1. m. ² represents an integer of 0 or 1. Further, in the formula (x), when m ² is 2 or more, the repeating unit can take a plurality of different repeating units.

As monovalent hydrocarbon groups having 1 to 20 carbon atoms in Z ^{1 to} Z ^{8 of} the structural units represented by the general formulas (viii), (ix) and (x), and X in the general formula (vii), Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and decyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group and allyl group, aryl groups such as phenyl group and tolyl group, And an aralkyl group. These groups may contain various functional groups such as epoxy groups, carboxyl groups, carboxylic anhydride groups, amino groups and mercapto groups as substituents. More preferably, it is a C1-C8 alkyl group, an alkenyl group, or an aryl group, and especially a C1-C4 alkyl group, such as a methyl group, an ethyl group, and a propyl group, a vinyl group, or a phenyl group is preferable.

  When the silicone compound has a plurality of siloxane units, they can take any form of random copolymerization, block copolymerization, and tapered copolymerization.

  In the component C of the present invention, when at least the amount of the aromatic group of the above condition (I) is not satisfied, the amount of Si—H group in the compound (hereinafter, simply referred to as “Si—H amount”) may be used. ) Is required to be 0.1 to 1.66 mol / 100 g. When the amount of Si—H is within such a range, good foaming characteristics are exhibited due to a decrease in surface tension, affinity with supercritical carbon dioxide, and an appropriate crosslinking effect. The amount of Si—H is more preferably in the range of 0.12 to 1.2 mol / 100 g, and still more preferably in the range of 0.15 to 1.0 mol / 100 g. When the amount of Si-H exceeds the upper limit, the surface tension is further lowered, but the reaction is difficult to control, and the appearance of the molded product may be deteriorated or the foam may be unstable. Therefore, even if the C component satisfies the condition (I), the Si—H amount is preferably not more than the above upper limit. On the other hand, when the amount of Si—H is below the lower limit, the compatibility with a suitable A component such as a polycarbonate resin tends to decrease. However, since this point is canceled if the condition (I) is satisfied, the lower limit may be satisfied if the condition (I) is satisfied, but it is more preferable that the condition (II) is satisfied. It is a silicone compound.

Further, the Si-H amount referred to here means the number of moles of the Si-H structure contained per 100 g of the silicone compound. This is the volume of hydrogen gas generated per unit weight of the silicone compound by the alkali decomposition method. It can be determined by measuring. For example, when 122 ml of hydrogen gas is generated per 1 g of the silicone compound at 25 ° C., the Si—H amount is 0.5 mol / 100 g according to the following formula.
122 × 273 / (273 + 25) ÷ 22400 × 100≈0.5

Further, as the C component silicone compound, it is preferable that the volatilization amount by a heat loss method at 105 ° C./3 hours is 18% or less. More preferably, the silicone compound has a volatilization amount of 10% or less. When the volatilization amount is larger than 18%, the volatilization amount of the silicone compound at the time of producing the resin composition also increases, and the preform for producing the foam tends to be defective.
As a silicone compound containing the structural unit shown by the said general formula, if it satisfy | fills the said conditions, it may be linear or may have a branched structure.

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units.
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _{1/2 , (CH 3) 2 (C} 6 H 5) SiO 1/2, (CH 3) (C 6 H 5) (CH 2 = CH) 1 functional represented by _R 3 _{SiO 1/2} of _{SiO 1/2,} etc. Siloxane unit D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) Bifunctional siloxane unit T unit represented by R ₂ SiO such as ₂ SiO: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) RSiO _3/2 such as SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 Trifunctional siloxane unit Q unit: tetrafunctional siloxane unit represented by SiO ₂

Specifically, the structure of the silicone compound used in the present invention has the following formulas: D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _p , M _{m D n Q q, M m} T p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Among these, preferable structures of the silicone compound are M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and more preferable structures are M _m D _n or M _m D _n. T _p .
(Here, the coefficients m, n, p, q in the above formula are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound) In the present invention, the preferred average degree of polymerization is in the range of 3-150, more preferably in the range of 3-80, still more preferably in the range of 3-60, and particularly preferably in the range of 4-40. The more uniform the range, the more uniform bubbles are obtained and the hue of the foam is excellent, and when any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient is Two or more types of siloxane units having different hydrogen atoms and organic residues can be used.)

  In the composition-I of the present invention, the dispersion state of the C component is important. If the dispersion of the silicone compound is not uniform, the foaming agent is highly concentrated in the silicone layer, and the interfacial adhesion tends to vary, and the generated bubbles are likely to be uneven and cracked. Important factors that determine the dispersion state include the amount of aromatic groups in the silicone compound and the average degree of polymerization.

  From this point of view, the silicone compound of the present invention is required to have an aromatic group content in the range of 10 to 70% by weight when at least the condition (II) is not satisfied. A preferable amount of the aromatic group is in the range of 15 to 55% by weight. If the amount of the aromatic group in the silicone compound is less than 10% by weight, the silicone compound is unevenly distributed and tends to be poorly dispersed, and if the amount of the aromatic group is more than 70% by weight, the compatibility tends to decrease. Therefore, the amount of the aromatic group is preferably 70% by weight or less even when the condition (II) is satisfied.

In addition, the amount of aromatic group herein refers to the ratio of the aromatic group represented by the general formula (vii) in the silicone compound, and can be determined by the following calculation formula.
(Calculation formula) Aromatic group amount = [A / M] × 100 (% by weight)
Here, A and M in the above formula represent the following numerical values, respectively.
A = Total molecular weight of all aromatic groups represented by the general formula (vii) contained in one molecule of the silicone compound M = Molecular weight of the silicone compound The silicone compound of component C may be used alone 2 You may use combining more than a seed.

  Such a silicone compound having an aromatic group and / or Si—H bond can be produced by a method known per se. For example, the target product can be obtained by cohydrolyzing the corresponding organochlorosilanes according to the structure of the target silicone compound and removing by-product hydrochloric acid and low-boiling components. In the case where the starting material is a silicone oil having an Si—H group or general formula (vii) in the molecule, other organic residues, cyclic siloxanes or alkoxysilanes, hydrochloric acid, sulfuric acid , By using an acid catalyst such as methanesulfonic acid, and optionally adding water for hydrolysis to advance the polymerization reaction, and then removing the used acid catalyst and low-boiling components in the same manner. A silicone compound can be obtained.

  The component C of the present invention satisfies the above conditions (I) and / or (II). Therefore, it is sufficient that either of the conditions (I) or (II) is satisfied, but in any case as described above, the amount of aromatic groups is preferably 70% by weight or less, and the amount of Si—H is 1.66 mol. / 100 g or less is preferable. Furthermore, it is preferable that both of the conditions (I) and (II) are satisfied.

  The composition ratio of the silicone component of component C is preferably 0.05 to 30 parts by weight with respect to 100 parts by weight of component A. The upper limit of the proportion of the component C is preferably 20 parts by weight, more preferably 10 parts by weight, and still more preferably 6 parts by weight. When the upper limit is exceeded, the mechanical properties of Composition-I are lowered, and as a result, the strength and heat resistance of the foam are likely to be lowered. On the other hand, when the component C is blended, it is effective if it is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and even more preferably 1 part by weight or more.

<Other additives>
Composition-I constituting the foam of the present invention is a resin composition containing a specific ratio of the A component and the B component as essential components, and more preferably also containing a C component. In addition to the B component and the C component, various additives that are usually blended in thermoplastic resins can be included.

(I) Phosphorus stabilizer It is preferable that various phosphorus stabilizers are further blended mainly for the purpose of improving the thermal stability at the time of molding of Composition-I. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Such phosphorus stabilizers can be used alone or in combination of two or more.

  Specifically, as the phosphite compound, for example, a trialkyl phosphite such as tridecyl phosphite, a dialkyl monoaryl phosphite such as didecyl monophenyl phosphite, a monoalkyl diaryl phosphite such as monobutyl diphenyl phosphite, Triaryl phosphites such as triphenyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol Such as diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Intererythritol phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite and 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4- Examples include cyclic phosphites such as (di-tert-butylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, and diisopropyl phosphate. Triphenyl phosphate and trimethyl phosphate.

  Preferred examples of the phosphonite compound include tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite. Tetrakis (2,4-di-tert More preferred are -butylphenyl) -biphenylene diphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Examples of the tertiary phosphine include triphenylphosphine.
The amount of the phosphorus stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, and 0.002 to 0.3 part by weight based on 100 parts by weight of the component A. Is more preferable.

(Ii) Antioxidant An antioxidant can be blended mainly for the purpose of improving the heat stability and heat aging resistance of the composition-I during the molding process. Such an antioxidant is preferably a hindered phenol stabilizer. Examples of the hindered phenol stabilizer include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3′-tert-butyl-5 ′). -Methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl) -4-hydroxy-5-methylphenyl) propionate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl } -2,4,8,10-tetraoxaspiro [5,5] undecane, N, N′-hexamethylenebis- (3,5 Di-tert-butyl-4-hydroxyhydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and tetrakis [ And methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane. All of these are readily available. Of these, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferably used. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types. The blending amount of these antioxidants is preferably 0.0001 to 0.05 parts by weight with respect to 100 parts by weight of component A.

(Iii) Ultraviolet Absorber Composition-I may be blended with an ultraviolet absorber for the main purpose of improving its ultraviolet resistance. Examples of such ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, cyclic imino ester compounds, and cyanoacrylate compounds known as ultraviolet absorbers. More specifically, for example, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (commercially available, CYTEC Corporation, CYASORB UV-5411 (product) Name)), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (commercially available from Ciba Specialty Chemicals KK) , TINUVIN234 (trade name)), 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] ( Examples of commercially available products include ADKASTAB LA-31 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd.), 2- (4,6-diphenyl-1,3) 5-triazin-2-yl) -5-[(hexyl) oxy] phenol (commercially available from Ciba Specialty Chemicals KK, TINUVIN 1577FF (trade name)), 2,2′-p- Phenylenebis (3,1-benzoxazin-4-one) (commercially available products include CEi-P (trade name) manufactured by Takemoto Yushi Co., Ltd. and CYASORB UV-3638 (trade name) manufactured by CYTEC) , And 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane (commercially available product) Are exemplified by UVINUL3030 (trade name) manufactured by BASF). The blending amount of the ultraviolet absorber is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 3.5 parts by weight, still more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the component A. Part.

(Iv) Ultraviolet absorber Composition-I can further contain 0.05-3.0 ppm (weight ratio) of a blueing agent in the composition. Such a bluing agent reduces the yellowness of Composition-I and makes it possible to give the foam a natural transparency or a high whiteness. Here, the bluing agent refers to a colorant that exhibits a blue or purple color by absorbing light of orange or yellow color, and a dye is particularly preferable. If the amount of the bluing agent is less than 0.05 ppm, the effect of improving the hue may be insufficient. On the other hand, if it exceeds 3.0 ppm, the coloring becomes strong, so that the blending amount of the bluing agent is not appropriate. A more preferred amount of bluing agent is in the range of 0.2 to 2.0 ppm in Composition-I. Representative examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer, and Polysynthrene Blue RLS manufactured by Clariant.

(V) Fluorescent dye Composition-I containing a fluorescent brightener-I has higher light reflectivity and natural transparency, and contains a fluorescent brightener and other fluorescent dyes that emit light-I Can have a design effect utilizing the luminescent color. Therefore, Composition-I can contain various fluorescent dyes for the main purpose of such effects.

  Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin. Of these, a coumarin fluorescent dye, that is, a fluorescent dye comprising a coumarin derivative is preferable. The amount of the fluorescent dye (including the fluorescent brightening agent) is 0.0001-3 parts by weight, preferably 0.0005-1 part by weight, more preferably 0.0005-0. 5 parts by weight, more preferably 0.001 to 0.5 parts by weight, particularly preferably 0.001 to 0.1 parts by weight.

(Vi) Release agent Composition-I may contain a release agent. As the release agent, for example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), Paraffin wax, beeswax and the like are preferably exemplified. Among such release agents, there are also components contained in the B component such as fatty acid esters. However, such a fatty acid ester has a weak effect as a surfactant used in the present invention, and the B component particularly suitable in the present invention is a fluorine-based surfactant. In the composition-I of the present invention, when such a fluorosurfactant is used as the B component, a small amount of a fatty acid ester can be contained as a release agent. Furthermore, the composition-I can contain a small amount of a silicone compound or fluorine oil that does not belong to the B component or the C component such as polydimethylsiloxane or polyfluoroalkyl ether as a release agent.

  Among such release agents, saturated fatty acid esters, particularly partial esters and / or full esters of higher fatty acids and polyhydric alcohols are preferred. Full esters are particularly preferred. Here, the higher fatty acid refers to an aliphatic carboxylic acid having 10 to 32 carbon atoms, and specific examples thereof include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid). ), Heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, docosanoic acid, hexacosanoic acid and other saturated aliphatic carboxylic acids, as well as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaene Mention may be made of unsaturated aliphatic carboxylic acids such as acids and cetoleic acid. Among these, the aliphatic carboxylic acid preferably has 10 to 22 carbon atoms, and more preferably has 14 to 20 carbon atoms. In particular, saturated aliphatic carboxylic acids having 14 to 20 carbon atoms, particularly stearic acid and palmitic acid are preferred. The aliphatic carboxylic acid such as stearic acid is usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Also in the saturated fatty acid ester, ester compounds obtained from stearic acid or palmitic acid which are produced from such natural fats and oils and are in the form of a mixture containing other carboxylic acid components are preferably used.

  On the other hand, as a polyhydric alcohol which is a structural unit of saturated fatty acid ester, a C3-C32 thing is more preferable. Specific examples of such polyhydric alcohols include glycerin, diglycerin, polyglycerin (for example, decaglycerin), pentaerythritol, dipentaerythritol, diethylene glycol, propylene glycol, and the like.

The acid value in the saturated fatty acid ester of the present invention is preferably 20 or less (can take substantially 0), and the hydroxyl value is more preferably in the range of 20 to 500 (more preferably 50 to 400). Further, the iodine value is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.
The content of the release agent is 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the component A. Within such a range, good mold release properties during molding of Composition-I and good hue of the foam are compatible.

(Vii) Light diffusing agent and light-reflective white pigment The foam of the present invention can be used as a light-diffusing material or a light-high reflecting material when it has fine bubbles. For the purpose of effectively improving or adjusting the light diffusion effect and the light reflection effect, the composition-I can contain a light diffusing agent and a white pigment. Examples of the light diffusing agent include polymer fine particles (preferably acrylic crosslinked particles and silicone crosslinked particles having a particle size of several μm), low refractive index inorganic fine particles, and composites thereof, and the ratio thereof is 100 parts by weight. The amount is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight based on the A component. The white pigment is particularly preferably a titanium dioxide pigment, and the proportion thereof is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight based on 100 parts by weight of the component A.

(Viii) Other dyes / pigments In addition to the bluing agent and the fluorescent dye, various dyes / pigments can be used for Composition-I. Particularly preferred are dyes. As dyes, perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindo Examples thereof include linone dyes and phthalocyanine dyes. Furthermore, metallic pigments, pigments exhibiting interference colors, and the like can also be blended. When such a dye / pigment is contained, the proportion is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, based on 100 parts by weight of the component A.

(Ix) Melt Elasticity Modifier Composition-I can contain a melt elasticity modifier. Such a modifier can improve melt elasticity and, as a result, increase resistance during bubble growth and suppress bubble breakage. As a result, a finer foam is provided. Such a modification effect of melt elasticity is basically obtained by a polymer having a high molecular weight, and in the case of a polymer or copolymer of an ethylenically unsaturated compound, its weight average molecular weight is 1 million to 20 million, more preferably 200 10,000 to 10 million are suitable. Representative examples of the polymer or copolymer of the ethylenically unsaturated compound include polyethylene, polystyrene, polymethyl methacrylate, poly (acrylonitrile-styrene) copolymer, poly (styrene-maleic anhydride) copolymer, and polytetrafluoroethylene (PTFE). The The composition ratio of the melt elasticity modifier is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight based on 100 parts by weight of the component A. In particular, the poly (acrylonitrile-styrene) copolymer having good compatibility is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight. PTFE inferior in compatibility is preferably 0.01 to 0.5 parts by weight, more preferably 0.01 to 0.1 parts by weight or less.

(X) Others Composition-I can contain a compound having heat-absorbing ability. Examples of the compound include phthalocyanine-based near infrared absorbers, metal oxide-based near infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, and metal boride-based near infrared rays such as lanthanum boride, cerium boride and tungsten boride. Preferred examples include various metal compounds having excellent near-infrared absorption ability such as an absorber, and carbon filler. These can be used alone or in combination of two or more. When a phthalocyanine-based near infrared absorber is included, the proportion is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, based on 100 parts by weight of component A, Preferably it is 0.001-0.07 weight part. In the composition-I, the metal oxide near-infrared absorber, metal borate-based near infrared absorber, and carbon filler are preferably in the range of 0.1 to 200 ppm (weight ratio), more preferably in the range of 0.5 to 100 ppm. preferable.

In Composition-I, an amount of flame retardant that does not impair the object of the present invention can be used. In addition, although a part of B component and C component are well-known as a flame retardant of the thermoplastic resin represented by polycarbonate resin, these shall not be contained in this flame retardant. Examples of the flame retardant include brominated epoxy resin, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, monophosphate compound, phosphate oligomer compound, phosphonate oligomer compound, phosphonitrile oligomer compound, phosphonic acid amide compound, organic acid metal Examples thereof include salts (excluding B component) and silicone flame retardants (excluding C component), and one or more of them can be used. Each of these flame retardants can be blended in a known amount relative to the polycarbonate resin.
In composition-I, a small amount of a resin other than thermoplastic or a crosslinkable elastomer can be used as long as the object of the present invention is not impaired. Furthermore, Composition-I may contain a small amount of various inorganic fillers, flow modifiers, antibacterial agents, photocatalytic antifouling agents, photochromic agents, and the like.

<About the manufacturing method of a resin composition>
In producing the composition-I of the present invention, the production method is not particularly limited. For example, the component A, the component B, and a method of melt-kneading other components as necessary, the component A, the component B A method can be used in which components and other components as necessary are mixed with a solvent typified by methylene chloride to form a solution, and then the solvent is removed. Further, in such melt kneading and solution mixing, an inert gas or its supercritical fluid may be mixed as a part of or all of the foaming agent, separately from the foaming agent. Such an inert gas, especially carbon dioxide, especially its supercritical fluid, plasticizes Composition-I, improves the dispersion of the components and forms a good foam. Such fluids can also promote composition volatilization with uniform dispersion in the case of solution mixing, providing Composition-I and foams thereof with reduced residual solvent. The production of Composition-I may be a continuous method or a batch method, but a continuous method is more preferable.

  Specific examples of the melt kneading method include a Banbury mixer, a kneading roll, an extruder, and a static mixer. Examples of such an extruder typically include various single-screw extruders, twin-screw extruders, and multi-screw extruders having three or more axes, and among them, a twin-screw extruder is preferably exemplified. The ratio (L / D) of the screw length (L) to the diameter (D) in such a twin-screw extruder is in the range of 30 to 50 in general commercial products, and is easy to use in the present invention. However, an extruder having an L / D of 100 is also known at present, and an L / D extruder close to 100 can also be used in the present invention. The extruder may have a so-called tandem configuration in which a plurality of extruders are connected in series. As the extruder, in addition to the above-mentioned extruder, a shear shear type kneading disperser represented by “Miracle KCK” manufactured by Asada Iron Works, and melt kneading at a high shear rate represented by “HSE3000” manufactured by Imoto Seisakusho. Including machines. As the static mixer, in addition to the “PM series” manufactured by Noritake Co., a mixer composed of elements described in 2004-024992 and a mixer utilizing an extension fluid dispersion technique can be used. The mixing by the extension fluid dispersion technique is described in, for example, 2001-124691. Such a static mixer may be used alone or in combination with an extruder. When using a static mixer in an extruder, it is preferable to arrange such a static mixer after raising the pressure using a gear pump. The latter two of the static mixers can also be used in solution mixing.

  Furthermore, when not taking the method of impregnating the foamed agent into the molten resin, an extruder having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

When the raw materials are supplied to the extruder for producing the composition-I, the raw materials can be dry blended in advance. In addition, the component that becomes liquid or liquid by heating can be injected using a liquid injection device, and using such injection is preferable because stable supply and good dispersion can be obtained. For dry blending, premixing devices such as V-type blenders, Henschel mixers, mechanochemical devices, and extrusion mixers can be used, and spares obtained using extrusion granulators and briquetting machines as necessary. Granulation of the mixture can be performed.
When using a granular material such as the pellet of Composition-I, the resin discharged from the die of the extruder may be directly cut, and the obtained strand is cut by a pelletizer to be pelletized.

<About the manufacturing method of a foam>
The foam of the present invention is prepared by the step A, that is, the method of impregnating the composition-I with the gas under high pressure as (ia) the method of impregnating the molten composition-I, and (ib) Any method of impregnating the solid-state composition-I can be selected, and the latter method (ib) is particularly preferable. Further, such a gas is preferably an inert gas or a supercritical fluid thereof. Such a solid state refers to a state in which melt processing is difficult even when the softening temperature is exceeded. Accordingly, the upper limit of the temperature in the solid state is exemplified by a temperature 20 ° C. higher than the glass transition temperature (Tg (° C.)) of Composition-I. The temperature for impregnating the gas is preferably not more than Tg of Composition-I. On the other hand, the temperature during decompression is preferably in the range of (Tg + 10-4P) ± 15 (° C.). The gas impregnation may be performed at a temperature exceeding the above range and not more than Tg. In such impregnation, a pressure reduction treatment can be performed by lowering the temperature to a temperature preferable for pressure reduction. However, in order to more stably produce the foam of the present invention, the temperature at the time of impregnation is preferably substantially constant, and therefore the temperature at the time of gas impregnation is preferably the same as the preferable temperature at the time of depressurization.

  A foam is formed from the composition-I impregnated with the gas through the steps B and C. As such a bubble forming method, (ii-a) a method of continuously forming bubble nuclei and bubbles by reducing the pressure of the composition-I impregnated with the blowing agent to form bubbles, and (ii-b) Any method for forming bubbles by independently heating and generating bubbles nuclei after depressurization can be selected. Further, as a method of attaching to the foam, (iii-a) a method of attaching before impregnation with the foaming agent, (iii-b) a method of attaching at the time of decompression, and (iii-c) further heating after the decompression. Any of the methods attached can be selected. In the method (iii-c), bubbles may or may not grow at that time.

Preferable specific examples in the method of impregnating the above-mentioned gas into the composition-I, the method of forming bubbles, and the method of molding into a foam are as follows.
(1) Combination (ib) + (ii-a) + (iii-a): This combination is typified by a method in which a molded product is impregnated with gas and then decompressed and foamed. In the case of foaming, free expansion is performed. In general, since a molded product expands uniformly three-dimensionally, it can have a shape similar to a shape previously formed.

  (2) Combination (ib) + (ii-a) + (iii-b): In this combination, a preformed composition-I molded body is impregnated with gas, and the pressure is reduced in the mold. It is represented by the method of attaching when foaming. The combination also includes a method in which a gas is impregnated after being impregnated, and then bubbles are generated or further grown in a free expansion state. Such a method is preferably used in the case of a resin that is sufficiently plasticized and melted by gas impregnation.

  (3) Combination (ib) + (ii-b) + (iii-a): Such a combination is obtained by impregnating a molded product with a gas and then reducing the pressure to generate bubble nuclei and further softening by heating. It is represented by a method of growing bubbles in an expanded state.

  (4) Combination (ib) + (ii-b) + (iii-b): In such a combination, the molded body of the pre-molded composition-I is impregnated with gas and then depressurized in the mold. It is represented by a method in which bubbles are sometimes grown or bubbles are grown in a free expansion state by molding a gas-impregnated molded body in a mold and then depressurizing and further softening by heating.

  (5) Combination (ib) + (ii-b) + (iii-c): This combination is obtained by impregnating a molded article of the pre-molded composition-I with a gas, reducing the pressure, and further heating. It is represented by the method of softening and expanding and attaching. Such a molded body may be preliminarily placed in the mold for attachment, or may be separately introduced into the mold for final attachment, and the former mold has a movable structure for the preliminary attachment. It may have a structure that becomes a mold for final attachment.

<Method of impregnating composition-I with foaming agent>
A method for impregnating the above-mentioned (ib) solid-state composition-I (hereinafter sometimes simply referred to as “resin” in this description) will be described. In such a method, the gas impregnation pressure is preferably in the range of 20 to 50 MPa as described above in the description of the constitution (4) of the present invention, and the gas is preferably injected in a supercritical state. Appropriate conditions are adopted so that the impregnation speed and the finer foaming can be achieved by this method. Since the gas impregnation rate depends on the plasticization state of the resin molecules, it is advantageous to increase the temperature in order to increase the impregnation rate. On the other hand, in order to refine the foaming, it is preferable that the glass transition temperature (Tg ′) of the resin plasticized by gas impregnation is close to the temperature at reduced pressure. The Tg ′ of the resin at the time of gas impregnation differs depending on the type of resin and the amount of gas impregnation (for example, depending on the treatment pressure), but the preferred treatment temperature in the present invention is (Tg + 10−4P) ± 15 ( ° C).

  The gas injection may be performed while the gas is sealed or circulated. In the impregnation of the resin in the solid state with the gas, it is preferable to impregnate the gas to a state as close to the saturation concentration as possible. However, if the time is too long, the productivity becomes inferior, and in the case of a resin that crystallizes, it becomes difficult to foam due to curing behavior such as crystallization.

<About the method of attaching to foam>
Various methods can be used for attaching the foam. In the combinations (1) and (3), the molding method is not particularly limited, and various methods known as thermoplastic resin molding methods can be used. Examples of such methods include injection molding, extrusion molding, blow molding, inflation molding, calendar molding, casting molding, hot press molding, rotational molding, and pultrusion molding. In injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, insert molding, in-mold coating molding, heat insulation mold molding, rapid heating and cooling mold molding as appropriate according to the purpose. A molded product can be obtained by using an injection molding method such as two-color molding, sandwich molding, and ultra-high speed injection molding, and a molding method combining these. In extrusion molding, multilayer extrusion molding, stretch molding and the like can be used, and such extrusion molding includes solid-phase extrusion molding.

  In the methods of the combinations (1) and (3), a non-foamed layer is usually formed on the surface layer of the molded body. Such a non-foamed layer is considered to occur because the surface molecular chains are in a highly oriented state and are difficult to deform. Molding methods that relieve strain on the surface layer, such as heat-insulating mold molding and rapid heating / cooling mold molding, can alleviate the orientation state and reduce the thickness of the non-foamed layer. Therefore, such a molding method can be used for such purposes. On the other hand, in the ultra-high speed injection molding, since the orientation state of the surface layer is high, the non-foamed layer is thick and the state in which the expansion ratio is suppressed is formed as a whole.

  In addition, the molded object which consists of this composition-I does not need to make all the foams, The aspect by which a part of molded object is foamed may be sufficient. For example, a portion where the composition-I is not formed on the surface of the molded body by a two-color molded body or a multilayer extruded body is exemplified. In addition, when there is a part other than this method where gas impregnation is desired to be suppressed, a prescription such as applying a masking film having low gas permeability to the part can be taken.

In the combination (5), examples of the attached mold include a method in which a molded body is introduced into a mold and heated, and a method in which a shape is defined by a heated roller or belt. Although it is preferable to grow or newly generate bubbles in such heating, there is no generation of bubbles, and it may be a die-shaped type to simply give the final shape.
In the combinations (2) and (4), the mold is a method of regulating expansion by reducing the pressure of the molded body introduced into the mold, or by extruding a solid-state molded body impregnated with gas at high pressure. A method is available.

<About the foam of the present invention>
The foam of the present invention satisfies that the length average diameter of the bubbles is 0.01 to 1 μm and the bubble number density is in the range of 10 ¹¹ to 10 ¹⁶ / cm ³ , Such length average diameter and bubble number density are measured as follows.

The cut surface of the foam is observed with a scanning electron microscope. The cut surface is cooled using a device such as a microtome in order to improve the smoothness of the surface. Such an observation image is a digital image having the number of pixels of 480 pixels in the vertical direction and 640 pixels in the horizontal direction, and has an observation magnification at which the diameter of the approximate bubble is about 20 pixels. At least 200 bubbles are measured at such a magnification to calculate a temporary value of the length average diameter. When the number of bubbles in one image is less than 200, a plurality of observation images are obtained so that the total number is 200. The provisional value is calculated by a method in which the obtained image is processed by an image analysis device, and the area of each bubble is converted into a circle-equivalent diameter. A numerical value corresponding to a length of 2 pixels or less is cut as noise. Obtain the observation magnification at which the provisional value calculated here is 10 pixels, obtain the observation image again at the observation magnification of the apparatus close to the magnification, and use the same procedure as the calculation of the provisional value from the image to The length average diameter Dw is obtained. If the observation magnification for calculating the provisional value is significantly different from the observation magnification for obtaining Dw, the same procedure is repeated with the latter magnification as a provisional value. Further, in this method, when the length average diameter is 1 μm, the observation magnification is appropriately 4000 times, and the length cut as noise at that time is 0.1 μm. The average length Dw of the bubbles is calculated by dividing the sum of the squares of the obtained bubble diameters by the sum of the bubble diameters. When the observation area is Sa (μm ² ) and the total area of bubbles is Sc (μm ² ), the area ratio occupied by the bubble part in the cut surface (observation surface) is S (%). Sc / Sa) × 100 (%).

前記式（１）において、Ｎ（個／ｃｍ^３）は気泡数密度を、ρ_ｆ（ｇ／ｃｍ^３）およびρ_ｐ（ｇ／ｃｍ^３）はそれぞれ発泡体および組成物−Ｉの密度を、Ｄｗ（ｃｍ）は前記気泡の長さ平均直径（但し（２）式における単位はｃｍである）を表す。 The bubble number density N is a value calculated by the following formula (1).

In the formula (1), N (number / cm ³ ) is the bubble number density, ρ _f (g / cm ³ ) and ρ _p (g / cm ³ ) are the density of the foam and the composition-I, respectively. Dw (cm) represents the length average diameter of the bubbles (however, the unit in the formula (2) is cm).

The volume fraction of the bubbles in the foam of the present invention is not particularly limited, but is preferably 0.5 to 50%, more preferably 3 to 25%, and still more preferably 5 to 20%. Since the foam of the present invention can have fine and uniform air bubbles, it is possible to improve the toughness represented by the elongation at break using such air bubbles as a craze generation point. That is, it is possible to exert an excellent effect in characteristics that are completely unrelated to the light weight expected of a normal foam. The volume fraction of bubbles is (1- (ρ _f / ρ _p )) × 100 (% using ρ _f (g / cm ³ ) and ρ _p (g / cm ³ ) in the formula (2). ).

  The foam of the present invention can have fine and uniform bubbles at high density, and can be used in a wide range of industrial fields due to such characteristics. The foam of the present invention can provide a resin member excellent in toughness represented by tensile fracture nominal strain, and the member can be used in a wide variety of industrial fields. The water absorption rate of the foam having such a foaming ratio is lower than that of a non-foamed molded article even when immersed in water at 23 ° C. for 120 days. The water absorption rate of the foam corresponds to the amount of water absorbed by the resin excluding the bubbles, indicating that water is not absorbed by the bubbles. That is, it is possible to provide a resin member having low water absorption, light weight and high toughness.

In addition, the foam of the present invention is larger than the above because, particularly when the component A is a polycarbonate resin, the resin can have both the good impact resistance inherent in such a resin and the impact absorption capability of the foamed molded product. An effective shock absorber can be provided even within the range of the expansion ratio. Utilizing the above characteristics makes it possible to provide an effective composite material. In fields that make use of lightness, in addition to various structural materials, it can be used for vibration plates of speakers and various oscillators.
Since the foam of the present invention can achieve a low dielectric constant due to the inclusion of bubbles, it can be used as a material for various electronic and electrical devices and can also be used for various separation membranes.

  On the other hand, the irregularities and high surface area of the fracture surface of the foam can also be used. The unevenness can be used for printing sheets, cell culture scaffolds, and the like. In the printing sheet, the ink placed on the surface is held in the recess, and the ink can be applied to a predetermined portion without spreading around. By utilizing such characteristics, it becomes possible to draw a thin line circuit with a conductive ink and form an electronic circuit. Further, it is excellent in physical anchor effect in various coatings, printing, plating, etc., and can be used as an adhesion improver. If the foam fraction of the present invention has a bubble fraction of about several percent, the bubbles are fine, so that they have sufficient light transmission, and are friendly even in fields where high light transmission is required.

  Further, according to a preferred production method, the foam of the present invention has closed cells and a surface layer having no foam. On the other hand, since such a suitable foam has a large distortion due to foaming almost uniformly, it is possible to provide surface irregularities by solvent cracks, or to make closed cells into open cells. Therefore, in the use of the above unevenness, unevenness due to such cracks can be used instead of the cross section of the foam.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

The following examples further illustrate the present invention.
(I) Evaluation Item (Ii) Density Measurement Using an electronic balance and a specific gravity measurement kit manufactured by METTLER TOLEDO Co., Ltd., the foam density ρ _f (g / cm ³ ) and before foaming treatment at a water temperature of 23 ° C. The density ρ _p (g / cm ³ ) of the test piece was measured. In addition, about the measurement of the tensile test piece, the cut piece of the chuck | zipper attachment part of this test piece was used.

(I-ii) SEM observation of cut surface Foamed test pieces were cut to a length of about 10 mm, and the individual cut pieces were sandwiched between clips and submerged in liquid nitrogen, and left for 5 hours. Thereafter, the test piece was taken out from the liquid nitrogen and attached to an HM360 type microtome manufactured by MICROM, and a work for obtaining a cut surface from the microtome was quickly performed. Platinum was vapor-deposited on the cut surface to obtain a sample for SEM observation. SEM observation was performed at a magnification based on the method described in the text. In this case, the surface layer of the foam does not contain bubbles and is in a non-foamed state, but this portion was observed without being observed.

(I-iii) Calculation of bubble diameter and bubble number density After clarifying the contrast of the hole portion of the digital image (length 480 pixels × width 640 pixels) obtained by the SEM observation, an image processing program (Mitani Corporation ( Image analysis was performed using WINROOF (manufactured by Co., Ltd.), and an operation for calculating the equivalent circle diameter from the area of the bubble cross section was performed. The length average diameter (Dw) was determined from the calculated value, and the bubble number density (pieces / cm ³ ) was determined from the numerical value of the density using the above-described equation (2). From this value, the value of S / Dw was calculated.

(II) Production of foam and results (II-1) Production of foam (1)
[Examples 1, 2, 4 to 9, 11 and Comparative Example 1]
In 100 parts by weight of various resin powders described in Tables 1 and 2, various additives listed in Tables 1 and 2 are added in various amounts, and a blueing agent (manufactured by Bayer: Macrolex Violet B) is 0.00007 wt. After blending uniformly in a blended amount and dry-blending uniformly, using a vent type twin screw extruder (KZW15-25MG manufactured by Technobel Co., Ltd.) under the conditions of screw rotation speed: 250 rpm, discharge amount: 2 kg / hr The mixture was melt kneaded to obtain pellets. The screw segment configuration had kneading zones formed by kneading disks upstream and downstream of the vent position. The degree of vacuum in the vent part was maintained at 3 kPa. The cylinder temperature and die temperature for each component A were 330 ° C. for PC-1, 290 ° C. for PC-2, 340 ° C. for PAR, and 290 ° C. for PPE.

  After drying the obtained pellets at 110 ° C. for 5 hours in a hot air circulating dryer, using an injection molding machine (J75EIII type manufactured by Nippon Steel), an injection speed condition of about 30 mm / sec, Plate-shaped test pieces having a length, width and thickness of 127 mm, 12.7 mm and 0.8 mm were formed. The cylinder temperature and mold temperature for each component A were 360 ° C. and 110 ° C. for PC-1, 310 ° C. and 100 ° C. for PC-2, and 310 ° C. and 100 ° C. for PPE, respectively.

  The obtained plate-shaped test piece was cut to a length of 60 mm from one end. One such test piece was placed in an aluminum frame. The frame had a square shape with an internal dimension of 52 mm long × 17 mm wide × 3 mm thick (a surface with a length of 52 mm and a thickness of 3 mm opened). The frames containing the test pieces were stacked and bundled with a SUS net and placed in a pressure vessel. The pressure vessel was cylindrical with an inner diameter of about 6 cm, a depth of about 16 cm and a capacity of about 500 mL.

  After sealing the pressure vessel, the inside of the vessel was purged with carbon dioxide gas at a temperature of 26 ° C., and then the temperature in the vessel was raised to 50 ° C. over 25 minutes by an electric heater incorporated in the vessel. The temperature in the container was measured with an inserted thermocouple. After reaching 50 ° C., carbon dioxide in a supercritical state was injected into the container, and the temperature also increased with an increase in the pressure in the container. After about 15 minutes, the temperature in the container reached 60 ° C. Here, the pressure was finally adjusted to 25 MPa, the valve was once closed, and the holding process was started. During this time, the state of pressure was observed, and when a decrease in pressure was observed, the operation of opening the valve again and injecting supercritical carbon dioxide was repeated, and the states of 25 MPa and 60 ° C. were maintained for 3 hours. After 3 hours, the release valve is suddenly opened, about 0.4 seconds until reaching from 25 MPa to 22 MPa, 3 seconds until reaching 20 MPa, 7 seconds until reaching 15 MPa, 13.5 seconds until reaching 10 MPa, 5 MPa The pressure was reduced for 37 seconds until reaching 0, and 52 seconds until reaching 0 MPa. The temperature of the container immediately after depressurization decreased to 26 ° C. by the cooling action of adiabatic expansion. Immediately after such pressure reduction, the pressure vessel was opened and the test piece was taken out. About 20 minutes later, the test piece was immersed in a silicone oil bath at 155 ° C. for 30 seconds to further foam. The density of the obtained foam was measured, and the bubble diameter was measured from SEM observation of the cut surface.

[Example 3 and Comparative Example 2]
Preparation of the test piece and installation in the pressure vessel were performed in the same manner as in Example 1. As in Example 1, the carbon dioxide gas was purged at room temperature and heated to about 70 ° C. over 40 minutes. Then, supercritical carbon dioxide gas was injected into the container, and after about 15 minutes, the temperature reached 80 ° C. The final adjustment was made to 20 MPa, and the holding treatment was started. Similarly, when the pressure dropped, the valve was opened and carbon dioxide gas was injected, and the state of 20 MPa and 80 ° C. was maintained for 3 hours. Thereafter, the valve was opened rapidly and the pressure was reduced by applying 1 second to 15 MPa, 3 seconds to 10 MPa, 8 seconds to 5 MPa, and 20 seconds to 0 MPa. After about 15 minutes, the pressure vessel was opened, and then the test piece was further foamed by being immersed in a 155 ° C. silicone oil bath for 30 seconds. The density of the obtained foam was measured, and the bubble diameter was measured from SEM observation of the cut surface.

[Example 10]
Preparation of the test piece and installation in the pressure vessel were performed in the same manner as in Example 1. However, the cylinder temperature and die temperature during extrusion were 340 ° C., the cylinder temperature during molding was 370 ° C., and the mold temperature was 110 ° C. As in Example 1, the carbon dioxide gas was purged at room temperature and heated to about 90 ° C. over 50 minutes. Then, supercritical carbon dioxide gas was injected into the container, and after about 15 minutes, the temperature reached 100 ° C. The final adjustment was made to 25 MPa, and the holding treatment was started. Similarly, when the pressure dropped, the valve was opened and carbon dioxide gas was injected, and the states of 25 MPa and 100 ° C. were maintained for 3 hours. Thereafter, the valve was opened rapidly, and the pressure was reduced by 0.9 seconds up to 20 MPa, 3 seconds up to 15 MPa, 6 seconds up to 10 MPa, and 28 seconds up to 0 MPa. After about 20 minutes, the pressure vessel was opened, and then the test piece was further foamed by being immersed in a silicone oil bath at 195 ° C. for 30 seconds. The density of the obtained foam was measured, and the bubble diameter was measured from SEM observation of the cut surface.

[Comparative Example 3]
Preparation of the test piece and installation in the pressure vessel were performed in the same manner as in Example 1. As in Example 1, the carbon dioxide gas was purged at room temperature and heated to about 90 ° C. over 50 minutes. Then, supercritical carbon dioxide gas was injected into the container, and after about 15 minutes, the temperature reached 100 ° C. The final adjustment was made to 15 MPa, and the holding treatment was started. Similarly, when the pressure dropped, the valve was opened and carbon dioxide gas was injected, and the states of 15 MPa and 100 ° C. were maintained for 3 hours. After that, the valve is suddenly opened, and it takes 0.4 seconds to reach 13 MPa, 2 seconds to reach 8 MPa, 6 seconds to reach 2 MPa, and 13 seconds to reach almost 0 MPa. The pressure was reduced. After about 20 minutes, the pressure vessel was opened, and then the test piece was further foamed by being immersed in a silicone oil bath at 155 ° C. for 30 seconds. The density of the obtained foam was measured, and the bubble diameter was measured from SEM observation of the cut surface.

  As is apparent from Tables 1 and 2, the composition containing the surfactant of the present invention has a bubble size that is greatly refined and a high bubble density due to high pressure conditions, and as a result, is not present in the past. It turns out that the favorable fine foam is formed. In addition, when a simple dumbbell was punched out from the test pieces after the foaming treatment of Examples 1 and 2 in the above, the tensile elongation values were 140% and 130%, respectively, which were extremely excellent. Characteristics were observed.

(III) Contents of each component indicated by symbols in Tables 1 and 2 (component A)
PC-1: Linear polycarbonate resin powder having a branched structure with a viscosity average molecular weight of 37,000 (manufactured by Teijin Chemicals Ltd .: Panlite C-1400WP)
PC-2: Linear polycarbonate resin powder having no branched structure having a viscosity average molecular weight of 22,500 (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WP)
PAR: Polyarylate resin (U polymer U-100, manufactured by Unitika Ltd.)
PPE: Polyphenylene ether resin (Asahi Kasei Co., Ltd. Zylon 600H)
HMWAS: acrylonitrile-styrene copolymer having a weight average molecular weight calculated by GPC measurement of 7 million (Brendex 869 manufactured by CROMPTON)

(B component)
F114: potassium perfluorobutane sulfonate (manufactured by Dainippon Ink & Chemicals, Inc .: MegaFuck F-114P)
F487: a compound represented by the above formula (iii) (CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ C ₈ F ₁₇ ) as a main component of the monomer and represented by the formula (iv) composed of dimethylsiloxane units. Type fluorine-containing surfactant containing a compound to be produced as a monomer (manufactured by Dainippon Ink Chemical Co., Ltd .: Megafax F-487)
F493: Fluorine composed of a perfluoro group-containing phosphate compound represented by the formula (ii-3) (Rf—X—O— is —OCH ₂ CH ₂ C ₈ F ₁₇ and —OM is —OH) Surfactant (manufactured by Dainippon Ink and Chemicals, Inc .: MegaFuck F-493)

(C component)
C-1: Silicone compound produced by the following method having a Si-H amount of 0.21 mol / 100 g, an aromatic group amount of 49% by weight, and an average degree of polymerization of 8.0. C-2: viscosity at 25 ° C. Methyl hydrogen polysiloxane having 20 mm ² / sec, Si—H content of 1.52 mol / 100 g, and aromatic group content of 0% by weight (KF99, Shin-Etsu Chemical Co., Ltd.)
C-3: Methylphenylpolysiloxane having a viscosity at 25 ° C. of 500 mm ² / sec, an Si—H amount of 0 mol / 100 g, and an aromatic group amount of 57% by weight (SH710 manufactured by Toray Dow Corning Silicone Co., Ltd.)

(Production of C-1)
A 1 L flask equipped with a stirrer, a cooling device, and a thermometer was charged with 301.9 g of water and 150 g of toluene, and cooled to an internal temperature of 5 ° C. A mixture of trimethylchlorosilane (21.7 g), methyldichlorosilane (23.0 g), dimethyldichlorosilane (12.9) and diphenyldichlorosilane (76.0) was charged into the dropping funnel and dropped into the flask over 2 hours while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged for 4 hours with stirring at an internal temperature of 20 ° C., then left to stand to remove the separated hydrochloric acid aqueous layer, added with 10% aqueous sodium carbonate solution, stirred for 5 minutes and then left to stand. The separated aqueous layer was removed. Then, it wash | cleaned 3 times with ion-exchange water, and it confirmed that the toluene layer became neutral. The toluene solution was heated to an internal temperature of 120 ° C. under a reduced pressure of about 2 KPa to remove toluene and low-boiling substances, and then insoluble materials were removed by filtration to obtain a silicone compound B-1 component.

(Other ingredients)
IRGP: Tris (2,4-di-tert-butylphenyl) phosphite (Ciba Specialty Chemicals: Irgafos 168)

Claims (5)

A foam formed from a composition (composition-I) containing 100 parts by weight of a thermoplastic resin (component A) and 0.001 to 30 parts by weight of a surfactant (component B), the length of the bubbles A foam satisfying that the average diameter is 0.01 to 1 μm and the cell number density is in the range of 10 ¹¹ to 10 ¹⁶ / cm ³ .   The foam according to claim 1, wherein the component A is at least one thermoplastic resin selected from the group consisting of a polycarbonate resin, a polyphenylene ether resin, and a polyarylate resin.   The foam according to claim 1, wherein the component B is a fluorosurfactant.   The foam according to any one of claims 1 to 3, wherein the foam is produced by a method of impregnating a solid composition-I with a supercritical fluid of an inert gas at a pressure of 20 to 50 MPa. body.   In the foam, S / Dw is 40 when the ratio of the area occupied by the bubble portion on the cut surface is S (%) and the average length of the bubbles in μm calculated from the cut surface is Dw. It is in the range of -500, The foam of any one of Claims 1-4.