CN1730539A - Resin composition and illuminating lamp shade made of the same - Google Patents
Resin composition and illuminating lamp shade made of the same Download PDFInfo
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- CN1730539A CN1730539A CNA2005100885523A CN200510088552A CN1730539A CN 1730539 A CN1730539 A CN 1730539A CN A2005100885523 A CNA2005100885523 A CN A2005100885523A CN 200510088552 A CN200510088552 A CN 200510088552A CN 1730539 A CN1730539 A CN 1730539A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V3/00—Globes; Bowls; Cover glasses
- F21V3/04—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings
- F21V3/06—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by the material
- F21V3/062—Globes; Bowls; Cover glasses characterised by materials, surface treatments or coatings characterised by the material the material being plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
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Abstract
The present invention provides a resin composition that has a good balance between diffusibility and transmission of visible rays, and is excellent in impact resistance and weather ability and has low frictional resistance and to provide a lighting cover formed from the resin composition. The resin composition comprises 60-90 wt% of (a) a methacrylic resin, 10-40 wt% of (b) an olefin resin, provided that the total of the components (a) and (b) is 100 wt%, and (c) a hydrogenated product of a copolymer consisting of at least one styrene polymer block and at least one conjugated diene compound block in an amount of 5-15 pts.wt. based on 100 pts.wt of the total of the component (a) and the component (b) wherein the difference in a value of melt flow rate (MFR) under the condition of a temperature of 230 DEG C and a load of 37.3 N between two materials; the component (a) and the component (b) is 10 or less and at least one kind of (d) a light diffusing agent is further blended in an amount of 0.1-15 pts.wt, based on 100 pts.wt. of the total of the components (a)-(c).
Description
Technical field
The balance that the present invention relates to a kind of diffustivity of visible light and perviousness is good, shock-resistance and weather resisteant is good, friction resistance is little resin combination and by its illuminating lamp shade of making.
Background technology
In recent years, in the residential lighting field, particularly for being directly installed on for the lighting fixtures on the top ceiling of ceiling light and so on, the designer trends of pursuing at present are: do one's utmost to relax that utensil all has happy sensation, all height low (reduced thickness) of utensil when installing on top ceiling from top ceiling outstanding impression, space.For this lighting fixtures, increase gradually to adopt and expand more laterally, and suppressed the slim design of height (reduction) than the outer peripheral portion of apparatus body.Obtain with the molding form under the situation of this slim shape lampshade, near the outer peripheral portion (expansion) wall thickness is compared the trend with attenuate with other parts, and be on the direction that outer peripheral portion (expansion) R reduces, in the restriction of design so there is the trend of strength reduction near the outer peripheral portion.The slimming of this lampshade, owing to can further develop down from now on, so adopt the low slightly resin combination of shock-resistance of the phenylethylene resin series used, that added light diffusing agent etc. of illuminating lamp shade in the past or acrylic resin and so on to form under the situation of lampshade, even it is contemplated that the performance of guaranteeing operational phase, for example when when transportation and maintaining operation, be easy to generate breakage (crackle) accidentally because of handling.
And under dwelling house has by the situation of the lighting fixtures of the structure of apparatus body clamping with the lampshade of ceiling lighting and so on, after lamp is lighted or is extinguished, about several minutes～tens of minutes, tend to produce abnormal sound (split, etc. sound) in the time, make the user produce unplessantness displeasure.This abnormal sound, not only the vibration because of stabilizer causes the lighting fixtures sympathetic response to produce continuously, and also can produce moment after lamp is lighted or extinguished, and the interval of generation is indefinite.
If trace the reason that this abnormal sound produces, will find the temperature that when light fixture is lighted or extinguish, can make lighting fixtures change (approximately normal temperature～50 ℃), apparatus body or lampshade produce thermal expansion, thermal contraction thus, owing to this moment of thermal expansivity difference separately, so the bound fraction at apparatus body and lampshade produces the moment skew, thereby produces abnormal sound.This is because the intensity of lampshade clamping fixture body is high more, and the static friction force on surface is big more when being in more than 40 ℃ by the lampshade that existing phenylethylene resin series or acrylic resin are made, and it is strong more that abnormal sound produces.
Yet the equipment that relevant illuminating lamp shade etc. adopted is attempted adopting the resin combination that will be dispersed with rubbery polymer to carry out the method (for example referring to patent documentation 1) of stacked grade up to now always.In this case, utilize the effect of allocating into of rubber elastomer, can improve the shock-resistance of molding.Yet molding surface friction of rest resistance more than 40 ℃ the time is big, can not suppress the abnormal sound when using as lighting.And also has the problem of manufacturing process's complexity, cost up.
And have the people to propose the resin combination (for example referring to patent documentation 2) that constitutes with ethylene series resin, polystyrene resin and alkene-styrene block copolymer, and the resin combination and the molding (for example referring to patent documentation 3) thereof that in this resin combination, have disperseed white additive or anti-marquis's agent.Adopt under the situation of this resin combination, utilize the effect of allocating into of ethylene series resin and alkene-styrene block copolymer, can improve shock-resistance, and the friction of rest resistance on molding surface is also low, so the abnormal sound might suppress to make illuminating lamp shade the time.Yet, for example when being used as the lampshade of above-mentioned the sort of slim shape, owing to lampshade and the approaching influence increase that makes light of light fixture, even therefore wherein be dispersed with anti-marquis's agent etc., be difficult to guarantee weather resisteant (discolouration of anti-marquis) in order to make the many polystyrene resin composition variable colors of the amount of allocating into, can to envision.And the tendency that the utensil temperature is risen is arranged, thereby can not fully suppress abnormal sound by slimming.
The somebody proposes a kind of resin combination by polyolefin resin and polymethacrylate and hydrocarbon resin (low-molecular-weight thermoplastic polymer) formation in addition, and in this resin combination, contain alpha-olefinic polymer part and α, the resin combination (for example referring to patent documentation 4) of the multipolymer of beta-unsaturated carboxylic acid ester polymer part.Adopt under the situation of this resin combination, by allocating polyolefin resin into, owing to can improve shock-resistance, the friction of rest resistance on molding surface is also low, so the abnormal sound might suppress to use as illuminating lamp shade the time.Yet, the hydrocarbon resin that in this resin combination, is contained (with coal tar as the hydrocarbon resin of raw material, decompose petroleum resin that petroleum fractions obtains, terpine resin etc.) influence under, not only the perviousness of visible light significantly reduces, and weather resisteant also had harmful effect, use so be not suitable as illuminating lamp shade.
Patent documentation 1: the spy opens flat 11-105207 communique
Patent documentation 2: the spy opens the 2002-234981 communique
Patent documentation 3: the spy opens the 2002-265723 communique
Patent documentation 4: the spy opens the 2003-113274 communique
In a word, still do not exist at present and can satisfy " diffustivity of visible light and perviousness balance " simultaneously, can prevent when using, be subjected to " abnormal sound is low " that heating such as light fixture causes that influence of temperature variation produces even be difficult to produce the illuminating lamp shade of " weather resisteant " of variable color near the light fixture use because of " shock-resistance " that careless manipulation etc. cracks as the lampshade of slim shape yet.
Summary of the invention
The present invention In view of the foregoing proposes, the resin combination that its purpose is to provide that the balance of a kind of diffustivity of visible light and perviousness is good, shock-resistance and weather resisteant are good, have low friction resistance, and have the diffustivity of good visible light and even the balance of perviousness is made the weather resisteant that also is difficult to the shock-resistance that cracks and is difficult to variable color under the situation of slim shape lampshade, can reduce the illuminating lamp shade that the influence of temperature change that causes because of the light fixture heating produces abnormal sound.
For reaching above-mentioned purpose, technical scheme 1 described invention is characterized in that, contains:
(a) the metha crylic resin composition of 60～90 weight %,
(b) with described (a) composition add up to 100 weight % 10～40 weight % ethylene series resin composition and,
(c) the hydrogenation thing composition of the multipolymer that constitutes by at least more than one styrenic block and at least more than one conjugated diene compound block,
The use level of described (c) composition is the resin combination of 5～15 weight parts with respect to resultant 100 weight parts of described (a) composition and described (b) composition,
Described (a) composition and two kinds of materials of described (b) composition are at 230 ℃ and loading 37.3N
The difference of the melt flow rate (MFR) under the condition (MFR) value is in below 10,
(d) allocate further that to measure 100 weight parts with respect to described (a) composition and even described (c) composition total be that the light diffusing agent composition of 0.1～15 weight part forms into.
The invention of technical scheme 2 is characterized in that (c) composition is the hydrogenation thing of maleic anhydride modified styrene-butadiene block copolymer (SEBS) in the invention of technical scheme 1 record.
The invention of technical scheme 3 is characterized in that (c) composition is the hydrogenation thing of styrene-isoprene block copolymer (SEPS) in the invention of technical scheme 1 record.
The invention of technical scheme 4 is characterized in that in the invention of technical scheme 1 record, in described (c) composition on the styrenic block at least in conjunction with a functional group.
The invention of technical scheme 5 is characterized in that being combined with twice-modified dose in the described functional group in the invention of technical scheme 4 records.
The invention of technical scheme 6 is characterized in that in conjunction with described (c) composition of a functional group, being the hydrogenation thing of amine modified phenylethylene-butadiene block copolymer (SBBS) at least in the invention of technical scheme 4 records.
The invention of technical scheme 7 is characterized in that being combined with described (c) composition of twice-modified dose in the invention of technical scheme 5 records, is the hydrogenation thing of maleic anhydride-amine modified phenylethylene-butadiene block copolymer (SBBS).
The invention of technical scheme 8 is illuminating lamp shades that the resin combination with technical scheme 1 any one record to the claim 7 is shaped and forms.
According to the present invention, the balance quality that can access a kind of diffustivity of visible light and perviousness is good, shock-resistance and weather resisteant is good, the resin combination of low friction resistance, and by its illuminating lamp shade that constitutes.More particularly, it is good to access a kind of balance quality with both only dark also not dazzling, as to be difficult to see visible lights such as light fixture damage diffustivity and perviousness, also have shock-resistance that is difficult to crack and the weather resisteant that is difficult to variable color even make under the situation of lampshade of slim shape, can reduce the illuminating lamp shade of the abnormal sound that the influence of temperature change because of the light fixture heating produces.
Embodiment
Below describe the present invention in detail.Metha crylic resin as (a) composition in the resin combination of the present invention, the polymkeric substance that the monomer polymerization that contains the above methyl methacrylate (hereinafter referred to as " MMA ") of 50 weight % is obtained more preferably contains the polymkeric substance that the monomer polymerization of the above MMA of 80 weight % obtains.Specifically, can enumerate as the polymethylmethacrylate of MMA homopolymer and the multipolymer that contains the above MMA of 50 weight % and can constitute with the unsaturated monomer of MMA copolymerization below 50 weight.
As can with the unsaturated monomer of MMA copolymerization, can enumerate MMA such as Jia Jibingxisuanyizhi, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate methyl acrylic ester in addition, esters of acrylic acids such as methyl acrylate, ethyl propenoate, cyclohexyl acrylate, phenyl acrylate, the unsaturated carboxylic acid of methacrylic acid, esters of acrylic acid, vinylbenzene, alpha-methyl styrene, vinyl cyanide, methacrylonitrile, maleic anhydride, phenyl maleimide, cyclohexyl maleimide etc.Also can adopt two or more these monomers in case of necessity.And above-mentioned multipolymer also can have Pyroglutaric acid unit or glutarimide unit.
As can with the unsaturated monomer of above-mentioned MMA copolymerization, the alkyl-acrylates of preferred methyl acrylate and so on.Under the situation with alkyl-acrylates and an amount of copolymerization of MMA,,, cause light penetration deterioration etc. in case increase the copolymerization amount then thermotolerance will reduce though raisings such as flowability when being shaped and heat-resisting decomposability and make shaping processability good.Contain as unsaturated monomer under the situation of alkyl-acrylates, as the monomer component in the above-mentioned multipolymer, alkyl acrylate is in below the 30 weight % with respect to the total amount of MMA and alkyl-acrylates, more preferably be in below the 15 weight %, further preferably be in below the 10 weight %.
And from the viewpoint of agent of low hygroscopicity, though,, will cause the deterioration of light penetration, the deterioration of weather resisteant etc. in case cinnamic copolymerization amount increases as preferably adopting vinylbenzene with the unsaturated monomer of MMA copolymerization.Adopt under the situation of vinylbenzene as unsaturated monomer,, vinylbenzene is in below the 50 weight %, more preferably be in below the 20 weight %, further preferably be in below the 15 weight % with respect to MMA and cinnamic total amount.
There is no particular restriction for the manufacture method of (a) composition, can adopt known method.For example can adopt various polymerization processs such as solution polymerization process, suspension polymerization, emulsion polymerization, block polymerization.Can use an amount of known azo based compound, superoxide, various mercaptan compound, terpenoid based compound etc. as polymerization starter or molecular weight regulator this moment.
One example of the commercially available metha crylic resin that can use as (a) of the present invention composition can be enumerated acrylic (ァ Network リ ペ ッ ト) MD (manufacturing of レ ィ ョ Application Co., Ltd. of Mitsubishi).
Ethylene series resin as (b) composition is alpha-olefins such as ethene, propylene, butene-1, amylene-1, hexene-1,3-methyl butene-1,4-methylpentene-1, octene-1, decylene-1, dodecylene-1, tetradecene-1, cetene-1, vaccenic acid-1, eicosylene-1, and the spy opens the homopolymer or the multipolymer of the olefines such as cyclic olefin of flat 2-115248 communique record.In addition, polyolefin resin also comprises the multipolymer of olefines and a small amount of other unsaturated monomer copolymerization, and the modifier that obtains by oxidation, sulfonation etc. of the homopolymer of this multipolymer and above-mentioned olefines or multipolymer.
Specific examples as (b) composition, the homopolymer of preferred ultrahigh molecular weight polyethylene(UHMWPE), high density polyethylene(HDPE), medium-density polyethylene, new LDPE (film grade), metallocene PE, half cross-linked type polyethylene, polypropylene etc., perhaps ethene, propylene, butene-1,3-methyl butene-1, the more than half multipolymer of 4-methyl butene-1 content, more preferably acrylic polymers such as alfon, propylene-ethylene block copolymer, propylene-ethylene random copolymers and composition thereof.
Can with other unsaturated monomers of the olefines copolymerization that constitutes (b) composition, can enumerate vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, methyl acrylate, MMA, maleic anhydride, the aryl maleimide, unsaturated organic acid or derivatives thereofs such as alkyl maleimide, vinyl esters such as vinyl acetate, vinylbenzene, aromatic ethenyl compounds such as vinyl toluene, vinyl trimethylammonium methoxy silane, vinyl silanes such as γ-methacryloxypropyl trimethoxy silane, Dicyclopentadiene (DCPD), 4-ethylidene-2-norbornylene, the 4-methyl isophthalic acid, the 4-hexadiene, the 5-methyl isophthalic acid, non-conjugated dienes such as 4-hexadiene etc.
Above-mentioned (b) composition can adopt the conventionally known method manufacturing of polymerization or modification.For example can adopt the method for No. 4900706 communique of United States Patent (USP), No. 4820775 record such as communique of United States Patent (USP) to obtain.And can extensively buy commercially available product, can therefrom suitably select the back to use.
The example of the commercially available ethylene series resin that can use as (b) of the present invention composition can be enumerated NOVATEC (ノ バ テ ッ Network) PP (Japanese Port リ プ ロ Co., Ltd. make), NIPOLONHARD (ニ Port ロ Application Ha-De) 6300 (eastern ソ one Co., Ltd. make).
(a) composition in the present composition and (b) proportioning between composition, when (a) composition and (b) total amount of composition are decided to be under the situation of 100 weight %, (a) lower limit of composition is in more than the 60 weight %, more than the preferred 70 weight %, its upper limit is in below the 90 weight %, below the preferred 80 weight %.And (b) lower limit of composition is in more than the 10 weight %, and more than the preferred 20 weight %, its upper limit is in below the 40 weight %, below the preferred 30 weight %.(a) under the very few situation of composition, rigidity reduces, and is easy to generate simultaneously to peel off and become fragile and bad.(a) under the too much situation of composition, not only can't improve shock-resistance, and abnormal sound suppresses effect and all become not enough, resistance to chemical reagents and shaping processability are also low, thereby also bad.
Constitute the styrenic block of hydrogenation thing of the multipolymer of forming by at least more than one styrenic block and at least more than one conjugated diene compound block of (c) composition, for example preferably from vinylbenzene, alpha-methyl styrene, neighbour-,-or p-methylstyrene, 4-propylstyrene, 2,4-dimethyl styrene, vinyl naphthalene, vinyl anthracene, Vinyl toluene, one or more materials that are polymerized to selecting among the monomers such as t-butyl styrene and toluylene, optimization styrene and alpha-methyl styrene in the monomer.
And conjugated diene compound block, for example be from 1,3-divinyl, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1, one or more materials that are polymerized of selecting in the monomers such as 3-hexadiene, preferred 1,3-butadiene, isoprene and combination thereof in the monomer.There is no particular restriction for the structure of conjugated diene compound block, and relevant 1,2-valence link or 3, and 4-valence link content does not have special restriction yet.
For above-mentioned (c) though in the hydrogenation thing of the multipolymer of composition the content of polystyrene block there is no particular restriction, its lower limit preferably is in more than the 10 weight %, more preferably more than the 15 weight %.And its upper limit preferably is in below the 80 weight %, more preferably below the 70 weight %.In a single day content crossed low just being easy to generate and peeled off, and isolates the state vitrify simultaneously, thereby bad.Content is in a single day too high will to become fragile, and is easy to generate crackle, so also bad.
The Determination on content of styrenic block, can be catalyzer for example in order to perosmic anhydride, use by the weight (wherein remove mean polymerisation degree be in about aromatic vinyl hydrocarbon polymer composition 30 below) of t-butyl hydroperoxide, obtain according to following formula with the resulting styrenic block composition of method (methods of people's " polymer science magazine " 1 volume 429 (1946) last records such as I.M.KOLTHOFF) of multipolymer oxygenolysis.
The content of styrenic block (weight %)=(as the weight of the polymkeric substance of weight/conduct (c) composition of styrenic block in the polymkeric substance of (c) composition) X100
And according to the ethylene series double-bond hydrogenation rate of the conjugated diene compound of copolymerization, can select arbitrarily according to purpose, be not particularly limited.Desire obtains under the situation of hydrogenation thing of the good multipolymer of thermostability and weather resisteant, should be at least more than the 50 weight % based on the hydrogenation rate of the two keys of conjugated diolefine ethylene series in the polymkeric substance, more than the preferred 80 weight %, more preferably more than the 90 weight %.And desire obtains under the situation of hydrogenation thing of the good multipolymer of thermostability and graft reaction, the lower limit of hydrogenation rate preferably is in more than the 3 weight %, more preferably more than the 5 weight %, more than the preferred especially 10 weight %, below the preferred 70 weight % of its upper limit, more preferably below the 65 weight %, below the preferred especially 60 weight %.Wherein, though be not particularly limited, preferably be in below the 50 weight %, more preferably below the 30 weight %, below the preferred especially 20 weight % about hydrogenation rate according to the two keys of aromatic series of the aromatic ethylene compound of copolymerization.Hydrogenation rate can adopt the peak of the two keys of butadiene hydrocarbon that infrared spectrophotometer (IR) obtains to record.
The copolymerization form of the multipolymer of this (c) composition can be enumerated random copolymers, segmented copolymer, graft copolymer and combination thereof, preferred block copolymer wherein, and block structure is not limited to diblock, three blocks and block etc. radially.And for the number-average molecular weight of this multipolymer there is no particular restriction, be generally 30,000～500,0000.
Conjugated diene compound block in the multipolymer of this in addition (c) composition, can also use other unsaturated monomers, vinylformic acid for example, methacrylic acid, toxilic acid, methylene-succinic acid, methyl acrylate, MMA, maleic anhydride, the aryl maleimide, unsaturated organic acid or derivatives thereofs such as alkyl maleimide, vinyl esters such as vinyl acetate, vinyl trimethylammonium methoxy silane, vinyl silanes such as γ-methacryloxypropyl trimethoxy silane, Dicyclopentadiene (DCPD), 4-ethylidene-2-norbornylene, the 4-methyl isophthalic acid, the 4-hexadiene, the 5-methyl isophthalic acid, the multipolymer that copolymerization such as non-conjugated diene such as 4-hexadiene form, and this multipolymer is through oxidation, the modifier of sulfonation etc.
As the example of the hydrogenation thing of this multipolymer, can enumerate the hydrogenation thing of the hydrogenation thing of styrene-butadiene copolymer (SBS, SEBS, SBBS), maleic anhydride modified styrene-butadiene copolymer, the hydrogenation thing of styrene-isoprene block copolymer (SEP, SEPS, SEEPS) etc.In these species, from performances such as weather resisteant and impact strength, flexural strengths, can suitably use the hydrogenation thing of maleic anhydride modified styrene-butadiene block copolymer (SEBS) or the hydrogenation thing of styrene-isoprene block copolymer (SEPS) especially.
Manufacture method as above-mentioned multipolymer can adopt known method and not have special restriction, for example can enumerate following anionic polymerization.That is to say, this method is as initiator with alkyl lithium compounds etc., in inert organic solvents such as normal hexane or hexanaphthene, make aromatic ethenyl compound, conjugated diene compound is polymerization successively, when reaching required molecular structure and molecular weight, after carrying out the addition of oxyethane or propylene oxide etc., add alcohols, carboxylic-acid, water etc. contain compound bearing active hydrogen stops polymerization, make the segmented copolymer that obtains in inert organic solvents such as normal hexane or hexanaphthene, by alkylaluminium cpd and cobalt, the hydrogenation catalysts such as Ziegler series catalysts that nickel etc. are formed exist down, 20～150 ℃ of temperature of reaction, carry out hydrogenation reaction under the conditions such as 1～150 kilogram/square centimeter of hydrogen pressure.
And (c) composition, it also can be the multipolymer that at least more than one styrenic block and at least more than one conjugated diene compound block are constituted, addition contains the polymer-modified hydrogenation thing that the properties-correcting agent (below be also referred to as properties-correcting agent one time) of functional group forms (below be also referred to as once polymer-modified etc.), and polymer-modified (in this specification sheets it is called twice-modified polymkeric substance, below once polymer-modified and twice-modified polymkeric substance is referred to as polymer-modified) that properties-correcting agent (in this specification sheets it being called twice-modified dose) is further obtained with this reaction such as once polymer-modified.Wherein, about the twice-modified aftermentioned that sees for details.Though there is no particular restriction for the content of the styrenic block of polymer-modified grade, is preferably 3～70 weight %, more preferably 5～60 weight %, preferred especially 5～45 weight %.
Styrenic block content is with respect to the ratio of the content of whole aromatic ethenyl compounds the ratio of styrenic block (below be called) in the above-mentioned polymkeric substance, should be in more than the 50 weight %, more than the preferred 60 weight %, more preferably more than the 70 weight %.Do not form the aromatic ethenyl compound of styrenic block in polymer-modified, both can distribute by homogeneous, can heterogeneity distribute yet in the multipolymer of conjugated diene compound and aromatic ethenyl compound part.And the part of the part of a plurality of aromatic ethenyl compound homogeneous distributions that in this polymkeric substance, can also coexist respectively and/or heterogeneity distribution.
The content of the block of styrenic, for example can be in order to above-mentioned perosmic anhydride as catalyzer, the weight (wherein remove mean polymerisation degree and be in about aromatic vinyl hydrocarbon polymer composition below 30) of the styrenic block composition that the method for multipolymer oxygenolysis is obtained with t-butyl peroxide is obtained according to following formula.
The content of the block of styrenic (weight %)=(all weight of the weight of styrenic block/whole vinyl-arenes in the vinyl-arene) * 100
Polymer-modified before the above-mentioned hydrogenation is on the active latter end of the multipolymer that is made of at least more than one styrenic block that obtains as polymerizing catalyst with organolithium compound and at least more than one conjugated diene compound block, an addition reaction properties-correcting agent described later obtains, and has for example structure shown in following formula (1)～(11).
[changing 1]
(A-B)
n-X …(1)
A-(B-A)
n-X …(2)
B-(A-B)
n-X …(3)
X-(A-B)
n …(4)
X-(A-B)
n-X …(5)
X-A-(B-A)
n-X …(6)
X-B-(A-B)
n-X …(7)
[(B-A)
n]
m-X …(8)
[(A-B)
n]
m-X …(9)
[(B-A)
n-B]
m-X …(10)
[(A-B)
n-A]
m-X …(11)
(in the following formula, A is styrenic block (below be called block A), and B is the block that is made of conjugated diene compound polymkeric substance and/or conjugated diene compound and aromatic ethenyl compound (below be called B block).N is the integer more than 1, is preferably 1～5 integer.M is the integer more than 2, preferred 2～11 integer.X represents to be combined with the residue of a properties-correcting agent of the atomic group that forms functional group described later.When with the anti-ying addition X of metallization described later (メ レ one シ ョ Application), X is combined on the side chain of A or A and B.And on X the structure of most bonded polymer chains, can be identical or different.) use among the present invention polymer-modified, also can be any mixture of the polymkeric substance represented by above-mentioned general formula.
Above-mentioned once polymer-modified be made in the active latter end addition of the polymkeric substance that obtains as polymerizing catalyst with organolithium compound the properties-correcting agent (properties-correcting agent) that contains functional group polymer-modified, further carrying out the polymer-modified of hydrogenation reaction, is to combine one at least to have the once polymer-modified of an atomic group of selecting at least from following group: hydroxyl, carboxyl, carbonyl, thiocarbonyl group, acyl halide group, anhydride group, the carboxylic acid group, the thiocarboxylic acid base, aldehyde radical, the sulfo-aldehyde radical, carboxylic acid ester groups, amide group, sulfonic group, sulfonate group, phosphate, phosphate-based, amino, imino-, cyano group, pyridyl, quinolyl, epoxy group(ing), the sulfo-epoxy group(ing), sulfino, isocyanate group, isothiocyanate group, silanol group, alkoxysilane group, silyl halide, the halogenation tinbase, the alkoxyl group tinbase, phenyl tinbase etc.
Once polymer-modified etc. in conjunction with atomic group with this functional group; can adopt following method to obtain; promptly by with the addition reaction of polymer active end; make this polymkeric substance addition have generation and be combined with a polymer-modified functional properties-correcting agent that has the atomic group of a functional group that from above-mentioned functional group, selects at least at least, perhaps in conjunction with the method for known method a properties-correcting agent of the atomic group of this protective group.As additive method, can enumerate organic alkali metal compounds such as making organolithium compound and polymer reaction (metallization reaction), the polymkeric substance of the organic alkali metal method of carrying out addition reaction that made above-mentioned properties-correcting agent and addition.Because properties-correcting agent kind difference, so in the stage that makes a properties-correcting agent reaction, hydroxyl or amino etc. generally also can form organic metal salt, handle but have compound bearing active hydrogen by water or alcohol etc. in this case, can make it form hydroxyl or amino etc.
In addition, when making the reactive terminal reaction of properties-correcting agent and polymkeric substance among the present invention, the polymkeric substance that part is not modified also can mix existence in once polymer-modified.In once polymer-modified, mix the ratio that has unmodified polymer, preferably be in below the 70 weight %, more preferably below the 60 weight %, below the preferred especially 50 weight %.
That uses among the present invention is particularly preferred once polymer-modified etc., is have a functional group that selects at least from hydroxyl, epoxy group(ing), amino, silanol group, alkoxysilane group once polymer-modified etc.
Among the present invention,, can enumerate the atomic group of from the atomic group shown in the general formula of following formula (1)～(25), selecting as the preferred atomic group that has a functional group that from hydroxyl, epoxy group(ing), amino, silanol group, alkoxysilane group, selects at least.
[changing 2]
-NR
1-R
5-OH …(12)
-N[R
5-OH]
2 …(13)
-NR
1-R
5-Si(OR
6)
3 …(14)
-N[R
5-Si(OR
6)
3]
2 …(15)
-O-R
5-Si(OR
6)
3 …(21)
(in the following formula, R
1～R
2Be alkyl, or have the alkyl of the carbonatoms 1～24 of the functional group that from hydroxyl, epoxy group(ing), amino, silanol group, alkoxysilane group, selects with hydrogen or carbonatoms 1～24.R
5Be the hydrocarbon chain of carbonatoms 1～48, perhaps at the hydrocarbon chain of carbonatoms 1～48 with the functional group that from hydroxyl, epoxy group(ing), amino, silanol group, alkoxysilane group, selects.In addition, at R
1～R
2Alkyl and R
5Hydrocarbon chain in, also can be with the combination beyond the hydroxyl, epoxy group(ing), amino, silanol group, alkoxysilane group in conjunction with elements such as aerobic, nitrogen, silicon.R
6It is the alkyl of hydrogen or carbonatoms 1～8.)
Among the present invention, in order to be combined with the once polymer-modified of an atomic group that has a functional group that selects at least from hydroxyl, epoxy group(ing), amino, silanol group, alkoxysilane group at least, an employed properties-correcting agent can be listed below.
As a properties-correcting agent, for example can enumerate four glycidyl group m-xylene diamine, four glycidyl group-1,3-diamino methylcyclohexane, four glycidyl group-right-phenylenediamine, four glycidyl group diaminodiphenyl-methane, diglycidylaniline, 2-glycidyl Ortho Toluidine.And, can also enumerate γ-glycidoxy ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy butyl trimethoxy silane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group tripropoxy silane, γ-glycidoxy propyl group three butoxy silanes, γ-glycidoxy propyl group triple phenoxyl silane, γ-glycidoxy propyl group methyl dimethoxysilane, γ-glycidoxy propyl group ethyl dimethoxy silane, γ-glycidoxy propyl group ethyl diethoxy silane.
And, for example also can enumerate γ-glycidoxy propyl group methyldiethoxysilane as a properties-correcting agent, γ-glycidoxy propyl group methyl dipropoxy silane, γ-glycidoxy propyl group methyl dibutoxy silane, γ-glycidoxy propyl group methyldiphenyl TMOS, γ-glycidoxy propyl-dimethyl methoxy silane, γ-glycidoxy propyl group diethyl Ethoxysilane, γ-glycidoxy propyl-dimethyl Ethoxysilane, γ-glycidoxy propyl-dimethyl phenoxy group silane, γ-glycidoxy propyl group diethyl methoxy silane, γ-glycidoxy propyl group methyl diisopropoxy silane, two (γ-glycidoxy propyl group) dimethoxy silane, two (γ-glycidoxy propyl group) diethoxy silane.
In addition, as a properties-correcting agent, for example also can enumerate two (γ-glycidoxy propyl group) dipropoxy silane, two (γ-glycidoxy propyl group) dibutoxy silane, two (γ-glycidoxy propyl group) hexichol TMOS, two (γ-glycidoxy propyl group) methyl methoxy base silane, two (γ-glycidoxy propyl group) methyl ethoxy silane, two (γ-glycidoxy propyl group) methyl-prop TMOS, two (γ-glycidoxy propyl group) methyl butoxy silane, two (γ-glycidoxy propyl group) methylenedioxy phenoxy base silane, three (γ-glycidoxy propyl group) methoxy silane, γ-methacrylic acid group propyl trimethoxy silicane, γ-methacrylic acid group propyl-triethoxysilicane, γ-methacrylic acid group propyl group methyltrimethoxy silane, γ-methacrylic acid group ethyl triethoxysilane, two (γ-glycidoxy propyl group) dimethoxy silane, three (γ-glycidoxy propyl group) methoxy silane.
And as a properties-correcting agent, for example can also enumerate β-(3, the 4-epoxycyclohexyl) ethyl-Trimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl-triethoxyl silane, β-(3, the 4-epoxycyclohexyl) ethyl-tripropoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl-three butoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl-triple phenoxyl silane, β-(3, the 4-epoxycyclohexyl) propyl group-Trimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl-methyl dimethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl-ethyl dimethoxy silane.
In addition as a properties-correcting agent, for example also can enumerate β-(3, the 4-epoxycyclohexyl) ethyl-ethyl diethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl-methyl dipropoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl-methyl dibutoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl-methyldiphenyl TMOS, β-(3, the 4-epoxycyclohexyl) ethyl-dimethyl methyl TMOS.
And as a properties-correcting agent, for example can also enumerate β-(3, the 4-epoxycyclohexyl) ethyl-diethyl Ethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl-dimethyl propylene TMOS, β-(3, the 4-epoxycyclohexyl) ethyl-dimethyl butyrate TMOS, β-(3, the 4-epoxycyclohexyl) ethyl-dimethyl phenoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl-diethyl methoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl-methyl diisopropoxy silane.
As a properties-correcting agent, can also enumerate 1 in addition, 3-dimethyl-2-imidazolone, 1,3-diethyl-2-imidazolone, N, N-dimethyl propyl urea, N-Methyl pyrrolidone etc.By making above-mentioned properties-correcting agent reaction, can obtain combining the polymer-modified of atomic group with a functional group that from hydroxyl, epoxy group(ing), amino, silanol group, alkoxysilane group, selects.The properties-correcting agent that contains functional group is carried out under the situation of addition reaction in the reactive terminal of the polymkeric substance with block A and B block, the reactive terminal of polymkeric substance independent block A is often arranged or block A is arranged and B block the two.
The consumption of an above-mentioned properties-correcting agent for 1 equivalent reactive terminal of polymkeric substance, should surpass 0.5 equivalent, be in below 10 equivalents, preferably surpasses 0.7 equivalent, below 5 equivalents, more preferably surpasses 1 equivalent, below 4 equivalents.
Twice-modified polymkeric substance of the present invention be make above-mentioned once polymer-modified and have reactive twice-modified dose of polymkeric substance that reaction obtains with this polymer-modified etc. functional group.Among the present invention, twice-modified dose of linking agent that preferably has two functional groups that from carboxyl, anhydride group, isocyanate group, epoxy group(ing), silanol group and alkoxysilane group, select at least.But, be under the situation of anhydride group when functional group, also can be anhydride group is one twice-modified a dose.Make under the twice-modified dose of situation with the reaction of properties-correcting agent, suitable with polymer-modified bonded 1 equivalent functional group once twice-modified dose, should be 0.3～10 mole, preferred 0.4～5 mole, more preferably 0.5～4 mole.
The method of properties-correcting agent and twice-modified dose of reaction is not particularly limited, can utilizes known method.For example, can enumerate mix method or of fusion in solvent with each composition dissolves or dispersing and mixing is reacted method etc.In with the method that each composition dissolves in solvent or dispersing and mixing is reacted, as solvent so long as can dissolve or disperse each composition just do not have a special restriction, except using except that aliphatic hydrocarbon, ester ring type hydro carbons, varsol such as aromatic hydrocarbon based, can also use the solvent that contains halogen, esters solvent, ether solvent etc.Make the temperature of each composition reaction in this method, be generally-10～150 ℃, preferred 30～120 ℃.The time of reacting required is different because of condition, generally is within 3 hours, is preferably several seconds～1 hour.Particularly preferred method is that interpolation makes its reaction for twice-modified dose in making once polymer-modified solution, obtains the method for twice-modified polymkeric substance.In this case, also can carry out neutralizing treatment, then with twice-modified dose of reaction to the solution of polymer-modified grade once.
Twice-modified dose specific examples, as linking agent with carboxyl, can enumerate aliphatic carboxylic acids such as toxilic acid, oxalic acid, succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, carboxylamine, cyclohexane diacid, ring pentanedioic acid, aromatic carboxylic acids such as terephthalic acid, m-phthalic acid, phthalic acid, naphthalene dicarboxylic acids, diphenyldicarboxylic acid, trimesic acid, trimellitic acid, pyromellitic acid etc.
As having twice-modified dose of anhydride group, can enumerate maleic anhydride, itaconic anhydride, pyromellitic acid acid anhydride, cis-4-hexanaphthene-1,2-dicarboxylic anhydride, 1,2,4,5-pyromellitic dianhydride, 5-(2,5-dioxo tetrahydroxy furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic acid-dicarboxylic anhydride etc.As twice-modified dose, can enumerate toluylene group diisocyanate, xylyl vulcabond, polyfunctional group aromatic isocyanate etc. with isocyanate group.
As having twice-modified dose of epoxy group(ing), except four glycidyl group-1, beyond 3-diamino methylcyclohexane, four glycidyl group-m-dimethylphenylene diamine, diglycidylaniline, ethylene glycol bisthioglycolate glycidyl, propylene glycol diglycidyl, the terephthalic acid diglycidyl ester acrylate etc., can also enumerate the epoxy compounds put down in writing as the properties-correcting agent that uses in order to obtain once polymer-modified grade etc.
As twice-modified dose, can enumerate the hydrolysate of the alkoxysilane compound containing trialkylsilyl group in molecular structure of being put down in writing as a properties-correcting agent that uses in order to obtain once polymer-modified grade etc. with silanol group.As having twice-modified dose of alkoxysilane group, except that two-(3-tri-ethoxy silylpropyl) four sulfanilamide (SN) (ス Le Off ァ Application), two-(3-tri-ethoxy silylpropyl) two sulfanilamide (SN), oxyethyl group hexanaphthene oligopolymer etc., can also enumerate the silane compound put down in writing as a properties-correcting agent that uses in order to obtain once polymer-modified grade etc.
Particularly preferred twice-modified dose is carboxylic acid or its acid anhydrides with two above carboxyls among the present invention, or has the properties-correcting agent of two above anhydride groups, isocyanate group, epoxy group(ing), silanol group, alkoxysilane group, for example maleic anhydride, pyromellitic acid acid anhydride, 1,2,4,5-pyromellitic dianhydride, inferior cresyl vulcabond, four glycidyl group-1,3-diamino methylcyclohexane, two-(3-tri-ethoxy silylpropyl) four sulfanilamide (SN) etc.
Example as the hydrogenation thing of the multipolymer that forms above-mentioned (c) composition, except that the hydrogenation thing of the hydrogenation thing of the hydrogenation thing of above-mentioned styrene-butadiene copolymer (SBS, SEBS, SBBS), maleic anhydride modified styrene-butadiene copolymer, styrene-isoprene block copolymer (SEP, SEPS, SEEPS), can also enumerate the hydrogenation thing etc. of styrene-butadiene block copolymer of hydrogenation thing, the maleic anhydride-amine modification of the styrene-butadiene block copolymer of amine modification.In these materials, the hydrogenation thing of the hydrogenation thing of hydrogenation thing from the viewpoint of character such as weather resisteant and shock strength and flexural strength, preferred especially hydrogenation thing, the styrene-isoprene block copolymer SEPS that adopts maleic anhydride modified styrene-butadiene block copolymer (SEBS)), the styrene-butadiene block copolymer (SBBS) of amine modification, the styrene-butadiene block copolymer (SBBS) of maleic anhydride-amine modification.
As can enumerating Off テ ッ Network M1911 (manufacturing of chemical Co., Ltd. of Asahi Chemical Industry), セ プ ト Application 2104 (manufacturing of Network ラ レ Co., Ltd.), Off テ ッ Network M10 (manufacturing of chemical Co., Ltd. of Asahi Chemical Industry), Off テ ッ Network N502 (manufacturing of chemical Co., Ltd. of Asahi Chemical Industry) as the commercially available examples of materials of (c) of the present invention composition use.
The proportioning of (c) composition in the resin combination of the present invention with respect to (a) composition of 100 weight parts and (b) total amount of composition, is 5～15 weight parts.Be lower than under the situation of 5 weight parts, peel off easily and isolate under the state form glassy, thereby bad.And in a single day surpass 15 weight parts, and rigidity is reduced, cost is increased, thereby bad.
In the resin combination of the present invention, (a) composition and (b) melt flow rate (MFR) (MFR) value of two kinds of composition materials of composition are meant the regulation according to JISK7210, the numerical value of measuring under the condition of 230 ℃ of resin temperatures and loading 37.3N.(a) composition and (b) melt flow rate (MFR) (MFR) value poor of two kinds of composition materials of composition are in below 10, preferably are in below 5.The difference of MFR value is in case surpass 10, when composition being carried out fusion mix, and mobile different because of (a) composition and (b) composition, feasible (a) composition can not dissolve each other with (b) composition.Therefore, be shaped as when the composition that can not fully dissolve each other under the situation of arbitrary shape, the molding that obtains or produce bad order because of uneven perhaps is easy to generate and peels off, and characteristics such as shock strength and flexural strength also reduces.
In resin combination of the present invention, adding at least, more than one promptly add a kind of or several combination backs as the light diffusing agent particulate of (d) composition.There is no particular restriction for the kind of this (d) composition, can suitably select known organic fine particles or inorganic particles according to working conditions.As organic fine particles, can enumerate cross-linked styrene and be particulate, crosslinked or high-molecular weight acrylic acid series particulate, cross-linked styrene-acrylic acid series particulate, cross-linked styrene-butadiene-based particulate, cross-linked silicone is that particulate, crosslinking silicone are that particulate, crosslinked urethane are that particulate, crosslinked melamine are particulate etc.As inorganic particles, can enumerate lime carbonate, Calcium Fluoride (Fluorspan), Potassium monofluoride, calcium phosphate, zinc oxide, sal epsom, barium sulfate, titanium oxide, potassium titanate, aluminium hydroxide, magnesium hydroxide, magnesiumcarbonate, aluminum oxide, mica, cerium oxide, Magnesium Stearate, lithium stearate, calcium stearate, Zinic stearas, barium stearate, crystalline form silicon oxide, unsetting silicon oxide, sheet glass, glass fibre, granulated glass sphere, clay etc., also can be that these inorganic particles have been implemented the surface-treated material.When using as the material of illuminating lamp shade, barium sulfate, lime carbonate, titanium oxide, the cross-linked silicone that preferably can give the light diffusing of appropriateness without detriment to visible light permeability are that particulate, crosslinking silicone are particulate.
The example of the commercially available light diffusing agent that can use as the present invention (d) composition can be enumerated AD barium sulfate (Japanese KCC makes).
The proportioning of (d) composition in the present composition is 0.1～15 weight part with respect to (a) composition of 100 weight parts with (b) total amount of composition.Be lower than under the situation of 0.1 weight part, disguised poor, can not obtain appropriate light diffusing.And in a single day surpass 15 weight parts, and will make the tone of resin combination and molding thereof become opaque and white, can not use as light transmission parts such as illuminating lamp shades, thereby bad.
In the resin combination of the present invention, in the scope of performance, can also utilize known method to make it contain various known additives in case of necessity.As this additive, can enumerate tinting materials such as dyestuff, pigment; Improve the developping agent or the dispersion agent of the dispersiveness usefulness of pigment or light diffusing agent; With acrylate, methyl acrylic ester as major ingredient and have the shock-resistance activator of the representatives such as rubbery polymer of core-shell-type Grafting Structure; The heat-resisting stabilizing agent weather resisteant activator of bulky amine, hindered phenolic, benzoate and so on; UV light absorber such as benzotriazole category, benzophenone, triazines, malonic ester class, salicylate class, amino acrylates class, oxanilide class; The phosphoric acid ester fire retardant; Palmitinic acid, Stearyl alcohol lipid lubricant; Organic system and inorganic series antibacterial agent; Static inhibitor etc.In addition, also can and use above-mentioned substance in case of necessity.
Resin combination of the present invention; can make with known method; promptly mix with the various compositions of mixing devices such as Henschel mixer, rotary blender with predetermined amount; utilize simple helix or double-screw extrusion machine, Banbury kneader etc.; fully fusion is mixed under 200～260 ℃ of temperature, is a granulated into granulating then.There is no particular restriction for the manufacture method of molding, can adopt known methods such as injection molding method, extruding formation method, flow forming method, compression forming method, or after utilizing extruding formation method to make sheet, adopt vacuum forming, the empty shaping of pressure, vacuum to press ageing methods such as empty shaping, pressure forming to make required shape again.
The illuminating lamp shade that is shaped with resin combination of the present invention for example is the lampshade of installing in the mode of the front that covers light fixture, is a kind ofly to spread with oyster white by light, and the light that light fixture is sent becomes soft, makes the illuminating lamp shade of the soft type of light fixture image.
Therefore, with the illuminating lamp shade that resin combination of the present invention is shaped, all light penetration preferably is in more than 40%, more preferably more than 50% and below 70%.All light penetration is if be in more than 40%, and then light can not become dark, and the light appropriateness that light fixture is sent is soft.And all light penetration is if be in below 70%, and then the light that not only light fixture is sent is soft, and can also obtain sufficient brightness.
This illuminating lamp shade can be suitable be used on the various lightings, the lampshade of usefulness such as ceiling light, pendent lamp, kitchen lamp, bathroom light, chandelier, floor lamp, suspended wall lamp, portable lighter, safety lamp, eaves lamp, door pillar lamp, corridor lamp, garden lamp, inlet lamp, footlights, stair light, the lamp that shows the way, warning lamp, shot-light, basic lamp, advertising lamp, signal lamp for example, and, be specially adapted to have by on ceiling lighting of the structure of lampshade body clamping etc. with automobile, the lampshade etc. of lamps apparatus for vehicle headed by two-wheeled etc.
Embodiment
Below based on embodiment and reference examples the present invention is described in further detail, but the present invention is not subjected to any restriction of these embodiment.The manufacture method of the illuminating lamp shade in embodiment and the reference examples at first is described.
Use rotary blender, hydrogenation thing with (a) metha crylic resin, (b) ethylene series resin, (c) at least more than one styrene polymer block and the multipolymer of at least more than one conjugated diene compound block formation, with (d) light diffusing agent, mix after being added into required additive.The double-screw extrusion machine of rotation in the same way with 47 millimeters of diameter of cylinder Φ, L/D=31.5 mixes its fusion under 240 ℃ of temperature condition, and online material is bathed (ス ト ラ Application De バ ス: after the water-cooled, cut off finish mix grain strand bath) with cutting machine.Then, the simple helix extrusion machine that usefulness diameter of cylinder Φ is 65 millimeters with the fusion of above-mentioned material grain, with the extruding of T mould, has obtained the sheet material of 750 millimeters of width, 1.8 millimeters of thickness under 240 ℃ of temperature condition.This sheet material is cut into 650mm * 650mm size, and empty the shaping pressed in heating, and obtaining a kind of main light transmission part thickness is the ceiling lighting illuminating lamp shade of 0.7～1.2 (mean thickness about 0.9) millimeter.
With in the above described manner among embodiment 1 to embodiment 4 and reference examples 1 to (a) to (d) composition of reference examples 6 is shown in table 1.And (a) to (d) composition of embodiment 5 to embodiment 8 is shown among the table 2.Is that the amount of allocating into of the hydrogenation thing of the multipolymer that constitutes of block is the ratio of the total amount of closing with respect to the metha crylic resin of conduct (a) composition of 100 weight parts with as the ethylene series resin of (b) composition as (c) composition in the table by styrenic block and conjugated diene compound.The amount of allocating into as the light diffusing agent of (d) composition is meant with respect to the ratio of 100 weight parts (a) composition to the total amount of (c) composition.
Table 1
| Reference examples 2 | The レ ィ ョ of acrylic resin acrylic MD001 Mitsubishi Application system | 50 | Acrylic resin NOVATEC PP EA9 Japan Port リ プ ロ system | 50 | Maleic anhydride modified hydrogenation styrene-butadiene block copolymer (SEBS) Off テ ッ Network M1911 Asahi Chemical Industry chemical system | 10 | 4.5 | Barium sulfate AD barium sulfate Japanization length of schooling | 3.0 |
| Reference examples 3 | The レ ィ ョ of acrylic resin acrylic MD001 Mitsubishi Application system | 70 | Acrylic resin NOVATEC PP EA9 Japan Port リ プ ロ system | 30 | Maleic anhydride modified hydrogenation styrene-butadiene block copolymer (SEBS) Off テ ッ Network M1911 Asahi Chemical Industry chemical system | 2 | 4.5 | Barium sulfate AD barium sulfate Japanization length of schooling | 3.0 |
| Reference examples 4 | The レ ィ ョ of acrylic resin acrylic MD001 Mitsubishi Application system | 70 | Acrylic resin NOVATEC PP EA9 Japan Port リ プ ロ system | 30 | Maleic anhydride modified hydrogenation styrene-butadiene block copolymer (SEBS) Off テ ッ Network M1911 (Asahi Chemical Industry's chemical system | 10 | 29 | Barium sulfate AD barium sulfate Japanization length of schooling | 3.0 |
| Reference examples 5 | The レ ィ ョ of acrylic resin acrylic MD001 Mitsubishi Application system | 70 | Acrylic resin NOVATEC PP EA9 Japan Port リ プ ロ system | 30 | Maleic anhydride modified hydrogenation styrene-butadiene block copolymer (SEBS) Off テ ッ Network M1911 Asahi Chemical Industry chemical system | 10 | 4.5 | Barium sulfate adds barium sulfate Japanization length of schooling | 0.0 5 |
| Reference examples 6 | The レ ィ ョ of acrylic resin acrylic MD001 Mitsubishi Application system | 70 | Acrylic resin NOVATEC PP EA9 Japan Port リ プ ロ system | 30 | Maleic anhydride modified hydrogenation styrene-butadiene block copolymer (SEBS) Off テ ッ Network M1911 Asahi Chemical Industry chemical system | 10 | 4.5 | Barium sulfate AD barium sulfate Japanization length of schooling | 18. 0 |
Table 2
Wherein the styrenic block content of the Off テ ッ Network M1911 shown in the table 1 is 30 weight %, and the block ratio of styrenic is 100 weight %, and hydrogenation rate is 100 weight %.And the styrenic block content of セ プ ト Application 2104 is 30 weight %, and the block ratio of styrenic is 100 weight %, and hydrogenation rate is 100 weight %.The styrenic block content of the Off of shown in the table 2 テ ッ Network MP10 is 30 weight %, and the block ratio of styrenic is 100 weight %, and hydrogenation rate is 70 weight %.And the styrenic block content of Off テ ッ Network N502 is 30 weight %, and the block ratio of styrenic is 100 weight %, and hydrogenation rate is 70 weight %.
And the test in embodiment and the reference examples and evaluation method are as follows.
(1) whole light penetrations
Use automatic recording spectrophotometer (Hitachi's system, U-4000 type), the total light transmittance that records under the wavelength of thick 1 millimeter of sample, 555nm is as data.
(2) light fixture image (light diffustivity)
The illuminating lamp shade that shaping is formed is installed in commercially available ceiling lighting (SUNX system, HHFZ5781X) on, bulb (Matsushita Electric Industries industry illumination Co., Ltd. system of lighting inboard will be set at, ッ ィ Application Pa (100 watts), white light) lights, from the visual observation of the illuminating lamp shade outside, according to following benchmark evaluation the difficulty opinion property of lamp image.
(determinating reference)
Zero: the shape that is difficult to see the shape image of lamp
△: the shape image that is easier to see lamp
X: the shape image of seeing lamp easily
(3) drop impact test (shock-resistance)
The illuminating lamp shade that shaping is obtained is installed in commercially available ceiling lighting (SUNX system, HHFZ5781X) on, with mounted illuminating lamp shade from the position of 50 centimetres of distance bed surface height (height on the vertical direction), the outer peripheral portion (expansion) that makes lampshade and bed surface keep vertical after, the outer peripheral portion of lampshade is fallen, with bed surface collision vertically substantially, visual observation whiting, disruptive are sent out into situation, according to following benchmark evaluation.
(determinating reference)
Zero: do not produce whiting, crackle
△:, do not crack though produced whiting
*: produced crackle
(4) abnormal sound test
The illuminating lamp shade that shaping is obtained is installed in commercially available ceiling lighting (SUNX system, HHFZ5781X) on, noise is lower than 24dB around, in about 20 ℃ atmosphere, behind the state placement certain hour of turning off the light, will be set at bulb (Matsushita Electric Industries industry illumination Co., Ltd. system of lighting inboard, ッ ィ Application Pa (100 watts), white light) light, (ONO SOKKI system LA-5120) has been measured the abnormal sound that produces in 30 minutes with phonometer at 1 meter of distance light fixture.And this light fixture is placed in about 20 ℃ atmosphere, place certain hour with the state of lighting a lamp after, lamp is extinguished, use with quadrat method and measured the abnormal sound that in 30 minutes, produces, and estimate according to following benchmark.
(condition determination)
Kinetic characteristic: fast
Compensated frequency characteristic: A characteristic
(determinating reference)
Zero: after lighting a lamp/turning off the light, the above abnormal sound of 24dB respectively produces below five times
△: after lighting a lamp/turning off the light, the above abnormal sound of 24dB respectively produces more than six times
(5)MFR
According to JIS K 7210, under 230 ℃ of resin temperatures, loading 37.3N condition, measure.
(6) weather resisteant
Sample is placed on is adjusted in 75 ℃ of heated air circulation type thermostatic baths under the atmosphere, under the state that mercuryvapour lamp is lighted, placed 15.(ス ガ test system SM-7) has been measured the aberration (Δ E*) of not test (N.T.) sample, is qualified below 3 to use the color colour-difference meter then.
To embodiment 1 to embodiment 4, and reference examples 1 to the evaluation result of reference examples 6 is shown among the table 3, and the evaluation result of embodiment 4 to embodiment 8 is shown among the table 4.
Table 3
| Total light transmittance (%) | The light fixture image | The whereabouts shock test | The abnormal sound test | Weather resisteant (Δ E*) | |
| Embodiment 1 | 64.3 | ○ | ○ | ○ | 2.33 |
| Embodiment 2 | 58.1 | ○ | ○ | ○ | 1.82 |
| Embodiment 3 | 51.9 | ○ | ○ | ○ | 2.01 |
| Embodiment 4 | 44.2 | ○ | ○ | ○ | 1.49 |
| Reference examples 1 | 75.3 | △ | △ | × | 1.18 |
| Reference examples 2 | 65.4 | ○ | △ | ○ | 2.30 |
| Reference examples 3 | 63.2 | ○ | × | ○ | 2.11 |
| Reference examples 4 | 62.5 | ○ | △ | ○ | 2.38 |
| Reference examples 5 | 85.5 | × | ○ | ○ | 2.62 |
| Reference examples 6 | 36.3 | ○ | ○ | ○ | 2.71 |
Table 4
| Total light transmittance (%) | The light fixture image | The whereabouts shock test | The abnormal sound test | Weather resisteant (Δ E*) | |
| Embodiment 5 | 66.1 | ○ | ○ | ○ | 2.12 |
| Embodiment 6 | 66.8 | ○ | ○ | ○ | 2.02 |
| Embodiment 7 | 66.5 | ○ | ○ | ○ | 2.23 |
| Embodiment 8 | 67.1 | ○ | ○ | ○ | 2.19 |
Claims (8)
1. a resin combination is characterized in that, contains:
(a) the metha crylic resin composition of 60～90 weight %,
(b) with described (a) composition add up to 10～40 weight % of 100 weight % ethylene series resin composition,
(c) the hydrogenation thing composition of the multipolymer that constitutes by at least one or its above styrenic block and at least one or its above conjugated diene compound block;
It is 5～15 weight parts that the use level of described (c) composition is measured 100 weight parts with respect to the total of described (a) composition and described (b) composition,
The difference of described (a) composition and two kinds of materials of described (b) composition melt flow rate (MFR) (MFR) value under 230 ℃, the condition of loading 37.3N is 10 or below it,
(d) further allocate into respect to described (a) composition to the total of described (c) composition and measure the light diffusing agent composition that 100 weight parts are 0.1～15 weight part.
2. according to the described resin combination of claim 1, it is characterized in that described (c) composition is the hydrogenation thing of maleic anhydride modified styrene-butadiene block copolymer (SEBS).
3. according to the described resin combination of claim 1, it is characterized in that described (c) composition is the hydrogenation thing of styrene-isoprene block copolymer (SEPS).
4. according to the described resin combination of claim 1, it is characterized in that, on the styrenic block of described (c) composition, be combined with at least one functional group.
5. according to the described resin combination of claim 4, it is characterized in that, in described functional group, be combined with twice-modified dose.
6. according to the described resin combination of claim 4, it is characterized in that described (c) composition that is combined with at least one functional group is the hydrogenation thing of amine modified phenylethylene-butadiene block copolymer (SBBS).
7. according to the described resin combination of claim 5, it is characterized in that described (c) composition that is combined with twice-modified dose is the hydrogenation thing of maleic anhydride-amine modified phenylethylene-butadiene block copolymer (SBBS).
8. one kind with claim 1 illuminating lamp shade that any one described resin combination is shaped and forms to the claim 7.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004230513 | 2004-08-06 | ||
| JP2004230513 | 2004-08-06 | ||
| JP2005122041A JP4938993B2 (en) | 2004-08-06 | 2005-04-20 | Resin composition and lighting cover comprising the same |
| JP2005122041 | 2005-04-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1730539A true CN1730539A (en) | 2006-02-08 |
| CN100338137C CN100338137C (en) | 2007-09-19 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100885523A Expired - Fee Related CN100338137C (en) | 2004-08-06 | 2005-08-04 | Resin composition and illuminating lamp shade made of the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4938993B2 (en) |
| KR (1) | KR100654181B1 (en) |
| CN (1) | CN100338137C (en) |
| TW (1) | TWI304827B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102328149A (en) * | 2011-09-05 | 2012-01-25 | 张家口北方对焊机有限公司 | Flash butt welding machine |
| CN102859260A (en) * | 2009-10-22 | 2013-01-02 | 光处方革新有限公司 | Solid-state light bulb |
| WO2014194670A1 (en) * | 2013-06-04 | 2014-12-11 | 南京华生皓光电科技有限公司 | Led ffu keel clean lamp and manufacturing process thereof |
| CN105220859A (en) * | 2015-08-31 | 2016-01-06 | 赵志恒 | A kind of Novel decorative board and preparation method thereof |
| CN105670149A (en) * | 2016-02-23 | 2016-06-15 | 东莞轩朗实业有限公司 | Photodiffusion master batch and photodiffusion plate containing the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100836572B1 (en) * | 2006-09-21 | 2008-06-10 | 주식회사 엘지화학 | Photo scattering polymer composition with advanced physical properties |
| KR102514986B1 (en) * | 2020-12-04 | 2023-03-29 | 킹스타라이팅 주식회사 | Germicidal lighting apparatus |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5181202A (en) * | 1975-01-14 | 1976-07-16 | Kawasaki Heavy Ind Ltd | IRIGUCHIDEGUCHIATSURYOKUOSEIGYOSURUJOKITAABIN |
| JPS5799846A (en) * | 1980-12-15 | 1982-06-21 | Matsushita Electric Works Ltd | Short circuit detection system for time-division multiplex transmission system |
| JP2617957B2 (en) * | 1987-07-09 | 1997-06-11 | 旭化成工業株式会社 | High-density polyethylene-based three-dimensional reticulated fiber and method for producing the same |
| JPH05345841A (en) * | 1992-06-16 | 1993-12-27 | Kuraray Co Ltd | Thermoplastic resin composition |
| JPH0649292A (en) * | 1992-08-03 | 1994-02-22 | Sumitomo Bakelite Co Ltd | Thermoplastic resin composition |
| JP2001131419A (en) * | 1999-11-05 | 2001-05-15 | Nippon Zeon Co Ltd | Light-diffusing composition |
| JP3911129B2 (en) * | 2001-02-09 | 2007-05-09 | アァルピィ東プラ株式会社 | Resin composition |
| EP1498455B1 (en) * | 2002-04-24 | 2011-08-24 | Kuraray Co., Ltd. | Polymer composition and uses thereof |
| JP5230056B2 (en) | 2004-04-14 | 2013-07-10 | 出光興産株式会社 | Light diffusing resin composition |
| JP2006045407A (en) | 2004-08-06 | 2006-02-16 | Matsushita Electric Works Ltd | Resin composition and molded body thereof |
-
2005
- 2005-04-20 JP JP2005122041A patent/JP4938993B2/en not_active Expired - Fee Related
- 2005-07-29 KR KR1020050069580A patent/KR100654181B1/en not_active IP Right Cessation
- 2005-08-04 CN CNB2005100885523A patent/CN100338137C/en not_active Expired - Fee Related
- 2005-08-08 TW TW094126836A patent/TWI304827B/en not_active IP Right Cessation
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102859260A (en) * | 2009-10-22 | 2013-01-02 | 光处方革新有限公司 | Solid-state light bulb |
| CN102859260B (en) * | 2009-10-22 | 2016-06-08 | 光处方革新有限公司 | Solid-state light bulb |
| CN102328149A (en) * | 2011-09-05 | 2012-01-25 | 张家口北方对焊机有限公司 | Flash butt welding machine |
| CN102328149B (en) * | 2011-09-05 | 2013-07-17 | 张家口北方对焊机有限公司 | Flash butt welding machine |
| WO2014194670A1 (en) * | 2013-06-04 | 2014-12-11 | 南京华生皓光电科技有限公司 | Led ffu keel clean lamp and manufacturing process thereof |
| CN105220859A (en) * | 2015-08-31 | 2016-01-06 | 赵志恒 | A kind of Novel decorative board and preparation method thereof |
| CN105220859B (en) * | 2015-08-31 | 2017-08-08 | 中山市优威斯特装饰材料有限公司 | A kind of dalle and preparation method thereof |
| CN105670149A (en) * | 2016-02-23 | 2016-06-15 | 东莞轩朗实业有限公司 | Photodiffusion master batch and photodiffusion plate containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI304827B (en) | 2009-01-01 |
| TW200607833A (en) | 2006-03-01 |
| KR100654181B1 (en) | 2006-12-06 |
| KR20060048946A (en) | 2006-05-18 |
| JP2006070243A (en) | 2006-03-16 |
| JP4938993B2 (en) | 2012-05-23 |
| CN100338137C (en) | 2007-09-19 |
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