CN1694919A - Ultraviolet absorber for synthetic resin and synthetic resin composition containing the same - Google Patents

Abstract

The present invention relates to an ultraviolet absorber for synthetic resins composed of a triazine compound represented by the general formula (I) shown below (wherein R represents an alkyl group having 1 to 4 carbon atoms, n is 0 or an integer of up to 2, and X represents a group selected from the consisting of group (a) to (d) shown below) (wherein R<1> represents an aliphatic group having 5 to 60 carbon atoms, which is an alicyclic group, an alkyl group having an alicyclic group at the terminal or in the chain thereof, an alkyl group having a branch, or a linear alkyl group, depending on the number of carbon atoms; R<2> represents an alkyl group having 1 to 18 carbon atoms or a (poly)alkyleneoxyalkyl group; R' represents an aliphatic diyl group having 5 to 60 carbon atoms; R and n have the same meanings as those described in the general formula (I) above).

Description

Synthetic resins is with UV light absorber and contain the compound resin composition of this UV light absorber

Technical field

The present invention relates to comprise have an ad hoc structure and with synthetic resins the synthetic resins UV light absorber of the triaizine compounds of good intermiscibility and the compound resin composition that contains this UV light absorber are arranged.

Technical background

Polyolefin resin such as polyethylene, polypropylene; Polycarbonate resin; Polyester resin such as polyethylene terephthalate, polybutylene terephthalate; Polystyrene, butadiene-styrene, ABS (acrylonitrile-butadiene-styrene copolymer), ACS styrene resins such as (vinyl cyanide-vinylchlorid-styrol copolymer); Polyamide-based resins such as nylon; Polyvinyl chloride, polyphenylene oxide, polymethylmethacrylate etc. are the synthetic resins of representative, can be widely used as materials such as various moldinies and fiber, film, coating in every field.

But, well-known, only by above-mentioned synthetic resins synthetic molding, can cause that deterioration, variable color and physical strength descend, and are unable to bear life-time service by the ultraviolet ray in natural light, the particularly natural light.

In order to prevent that these molding processing from the deterioration that resin causes because of light, being to be used alone or in combination UV light absorber and photostabilizer so far.The known triazine based compound of using is as UV light absorber, can bring into play good effect, for example, being reported in the spy opens flat 4-214785 communique, spy and opens flat 5-125248 communique, Te Kaiping-5-93089 communique, spy and open flat 10-95974 communique, Te Kaiping-10-147577 communique, No. the 2779981st, patent, spy and open 2000-313051 communique etc.

But the triazine based compound in the above-mentioned report and the intermiscibility of resin Composition and/or dispersed not enough can not provide enough additive effects.Use thermoplastic resin for the shaping processing of polycarbonate resin, polyolefin resin, polyester resin etc. especially, the problems referred to above are very outstanding.And, also has the problem of transparency difference picture albefaction, the muddiness etc. for polyolefin resin.

Thereby, the purpose of this invention is to provide with resin Composition have good intermiscibility or dispersiveness, and synthetic resins that enough additive effects can be provided with UV light absorber with contain the compound resin composition of this UV light absorber.

Summary of the invention

Present inventors further investigate, and found that,, with synthetic resins good dispersiveness is arranged, and excellent weathering resistance is provided as UV light absorber with the synthetic resins that comprises the triaizine compounds with ad hoc structure, have reached purpose of the present invention.

That is, first synthetic resins UV light absorber that the triaizine compounds that comprises that following general formula is represented is provided of the present invention,

In the general formula (I), R is that carbonatoms is 1～4 alkyl, and n is 0～2 integer, and X is the group that is selected from following (a)～(d),

In above-mentioned (a)～(d), R ¹Being that carbonatoms is 5～60 fatty group, is 5～8 o'clock at the carbonatoms of fatty group, R ¹For being selected from alicyclic radical and endways or have the group of the alkyl of alicyclic radical in the chain,

At carbonatoms is 9～19 o'clock, R ¹For being selected from the group that has the alkyl of alicyclic radical in alicyclic radical, end or the chain and have the alkyl of side chain,

At carbonatoms is 20～60 o'clock, R ¹For being selected from the alkyl that has alicyclic radical in alicyclic radical, end or the chain, having the alkyl of side chain and the group of straight chained alkyl;

R ²Be be selected from carbonatoms be 1～18 have a side chain or endways or have the alkyl of alicyclic radical and the group (carbonatoms also comprises alicyclic radical) of (many) alkoxyalkyls in the chain;

R ' is that carbonatoms is 5～60 aliphatics two bases, is 5～8 o'clock at the carbonatoms of fatty group, and R ' is for being selected from alicyclic radical and endways or have the group of the alkane 2 basis of alicyclic radical in the chain,

At carbonatoms is 9～19 o'clock, and R ' is selected from the group that has the alkane 2 basis of alicyclic radical in alicyclic radical, end or the chain and have the alkane 2 basis of side chain,

At carbonatoms is 20～60 o'clock, and R ' is the group that is selected from the alkane 2 basis of the alkane 2 basis that has alicyclic radical in alicyclic radical, end or the chain, the alkane 2 basis with side chain and straight chain.

Wherein identical in R, n and the above general formula (I).

The 2nd of the present invention provides the 1st described synthetic resins UV light absorber as the present invention, and wherein: the X in the described above general formula (I) is the group of using (a) or (d) representing.

The 3rd of the present invention provides as the 1st of the present invention or the 2nd described synthetic resins UV light absorber, wherein: at described general formula (I) with in general formula (I) in the represented group of X, n is 0.

The 4th of the present invention provides compound resin composition, and it is to mix 0.001～25 mass parts the present invention the 1st point～the 3rd described synthetic resins UV light absorber in middle any point in 100 mass parts synthetic resins.

The 5th of the present invention provides the 4th described compound resin composition as the present invention, and wherein: also mixing at least a hindered amine of 0.001～10 mass parts is photostabilizer.

The 6th of the present invention provides as the 4th of the present invention or the 6th described compound resin composition, and wherein: described synthetic resins is selected from polycarbonate resin, polyolefin resin, polyester resin.

Implement best mode of the present invention

Embodiments of the present invention below are described.

Synthetic resins of the present invention comprises the triaizine compounds with the represented structure of above general formula (I) with UV light absorber.

In the group of (a)～(d) that the X in above general formula (I) is represented, R ¹, R ' and R ²Intermiscibility and/or the dispersiveness of UV light absorber to synthetic resins is provided, and carbonatoms is big more, and its intermiscibility and/or dispersiveness are good more.If intermiscibility and/or good dispersity, even the stable ultraviolet resistance effect might as well when equivalent is mixed the ultraviolet radiation absorption base, but along with carbonatoms becomes big, the ratio that has the triazine skeleton of ultraviolet radiation absorption function in the molecule just diminishes, so can not obtain sufficient additive effect.

At R ¹, among the R ', alicyclic radical or branched-chain alkyl or alkane 2 basis are than the intermiscibility and/or the good dispersity of straight chained alkyl or alkane 2 basis, therefore, the former carbon atom can lack, having the alkyl of alicyclic radical or the carbonatoms of alkane 2 basis is 5～60, having the alkyl of side chain or the carbonatoms of alkane 2 basis is 9～60, and the carbonatoms of straight chained alkyl or alkane 2 basis is 20～60.

And R ²Carbonatoms be 1～18.

Illustrate that below the X in the triaizine compounds involved in the present invention is the situation of (a).

R ¹For alicyclic radical or endways or when having alicyclic radical in the chain, its carbonatoms is 5～60, more preferably 5～19.Triaizine compounds with alicyclic radical, its good heat resistance, therefore when making it have in mixing synthetic resins because of the good feature of processing temperature initial coloring.

As above-mentioned alicyclic radical or endways or have the R of alicyclic radical in the chain ¹, example can be enumerated following general formula (1) or (2) represented group preferably.And the alicyclic radical among the present invention is also included within the notion that has 1～2 unsaturated link(age) in the ring structure.

The carbonatoms that has 1～2 unsaturated link(age) in the formula in the ring A representative ring structure is 5～8 alicyclic radical, and Ra represents alkyl, and Rb represents alkane 2 basis, and P represents 0～4 integer, and the carbonatoms of whole group amounts to 5～19.

The object lesson of ring A can exemplify in above general formula (1) or (2): pentamethylene ring, cyclohexane ring, cyclooctane ring, bicycloheptane ring, bicyclohexane ring, bicyclooctane ring and the ring that contains 1～2 unsaturated link(age) in these ring structures.The object lesson of alkyl Ra can be enumerated: methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group etc.The object lesson of alkane 2 basis Rb can be enumerated: methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, octylene, inferior decyl etc.

Above-mentioned for alicyclic radical or endways or have the R of the alkyl of alicyclic radical in the chain ¹In, basic end has the alkyl of alicyclic radical can be enumerated: cyclopentyl, 2-cyclopentyl ethyl, 3-cyclopentyl propyl group, 4-cyclopentyl butyl, 5-cyclopentyl amyl group, cyclohexyl, 1-methylcyclohexyl, cyclohexyl methyl, 2-cyclohexyl ethyl, 3-cyclohexyl propyl group, 4-cyclohexyl butyl, 5-cyclohexyl amyl group, 8-cyclohexyl octyl group, 10-cyclohexyl decyl, suberyl, ring octyl group, dicyclohexyl, two suberyl, two ring octyl groups etc.

The alkyl that has alicyclic radical in chain can be enumerated: 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,4-Dimethylcyclohexyl, 2,5-Dimethylcyclohexyl, 2,6-Dimethylcyclohexyl, 3,4-Dimethylcyclohexyl, 4,5-Dimethylcyclohexyl, 4-ethyl cyclohexyl, 4-propyl group cyclohexyl, 4-isopropylcyclohexyl-, 4-butyl cyclohexyl, 4-tert-butylcyclohexyl, 4-hexyl ring octyl group, 4-cyclohexyl decyl, (4-methylcyclohexyl) methyl, 2-(4-ethyl cyclohexyl) ethyl, 3-(4-isopropylcyclohexyl-) propyl group etc.

In the triaizine compounds involved in the present invention, the compound N that these alicyclic radicals or the example more specifically that has the alkyl of alicyclic radical endways in the chain can be enumerated the following stated o.1～6.

The R of triaizine compounds involved in the present invention ¹When having the alkyl of side chain, its carbonatoms is 9～60.

In the case, R ¹For by described aliphatic carboxylic acid deutero-group.Derive and to enumerate for the aliphatic carboxylic acid of this group: 2-(3-methyl butyl)-7-methyloctanoic acid, 2-(1-methyl butyl)-5-methyloctanoic acid, the 2-hexyldecanoic acid, 2-heptyl capric acid, 2-(1,3,3-trimethylammonium butyl)-5,7, the 7-trimethylammonium is sad, 2-(3-methyl hexyl)-7-methyl capric acid, 2-octyl group dodecylic acid, 2-methyl arachic acid, 2-propyl group octadecanoic acid, 2-butyl octadecanoic acid, 2-methyl docosoic acid, 10-methyl docosoic acid, 2-amyl group octadecanoic acid, 2-methyl tricosanic acid, 3-methyl tricosanic acid, 22-methyl tricosanic acid, 20-ethyl docosoic acid, 18-propyl group hexacosanoic acid, 2-hexyl octadecanoic acid, 12-hexyl octadecanoic acid, 2-methyl Lignoceric acid, 3-methyl Lignoceric acid, 6-methyl Lignoceric acid, 10-methyl Lignoceric acid, 12-methyl Lignoceric acid, 14-methyl Lignoceric acid, 18-methyl Lignoceric acid, 23-methyl Lignoceric acid, 9-heptyl octadecanoic acid, 9-octyl group margaric acid, 24-methyl carboceric acid, 2-ethyl Lignoceric acid, 2-butyl docosoic acid, 2-hexyl arachic acid, 2-octyl group octadecanoic acid, 2-undecyl pentadecylic acid, 2-decyl hexadecanoic acid, 2-methyl hexacosanoic acid, 10-methyl hexacosanoic acid, 2-nonyl octadecanoic acid, 2-decyl octadecanoic acid, 2-undecyl octadecanoic acid, 2-dodecyl octadecanoic acid, 33-methyl gheddic acid, 20,20-dimethyl heneicosanoic acid, 13,16-dimethyl tricosanic acid, 14,17-dimethyl Lignoceric acid, 3,13,19-trimethylammonium tricosanic acid, 3,13-dimethyl pentacosoic acid etc.

Above-mentioned R ¹As the alkyl that side chain is arranged, from with synthetic resins good intermiscibility and/or dispersiveness are arranged and have ultraviolet radiation absorption can the ratio of benzotriazole skeleton consider, be advisable with carbon atom 9～19, be more preferably the represented carbonatoms of following general formula (3) and be 1-alkyl alkane-1-base of 9～19.

In the formula, R ³For the carbonatoms that side chain can be arranged is 4～17 alkyl, R ⁴For the carbonatoms that side chain can be arranged is 1～9 alkyl, R ³Carbonatoms compare R ⁴Carbonatoms many.

Has a R with above-mentioned ¹In when having the triaizine compounds of the alkyl of side chain to be used for polyolefin resin, be 14～19 to be advisable with carbonatoms turbidity is low, the compound resin composition of good penetrability because obtain, and is more preferably the side chain (R in the above general formula (3) ⁴) carbonatoms more than 3, good especially more than 5.

Above-mentioned preferred R ¹Base be have on the α position that the aliphatic carboxylic acid of side chain derives out group, there is the aliphatic carboxylic acid of side chain to enumerate on the described α position: 2-(3-methyl butyl)-7-methyloctanoic acid, 2-(1-methyl butyl)-5-methyloctanoic acid, 2-hexyldecanoic acid, 2-heptyl capric acid, 2-(1,3,3-trimethylammonium butyl)-5,7, the 7-trimethylammonium is sad, 2-(3-methyl hexyl)-7-methyl capric acid, 2-octyl group dodecylic acid etc.

R in the triaizine compounds involved in the present invention ¹The compound N that can enumerate the following stated for the more specifically example of alkyl with above-mentioned preferred form side chain o.7-11.

The R of triaizine compounds involved in the present invention ¹During for straight chained alkyl, its carbonatoms is 20～60.

In the case, R ¹Be the group of deriving out from described straight chain aliphatic carboxylic acid, the aliphatic carboxylic acid that derives described group can be enumerated: straight-chain carboxylic acids such as heneicosanoic acid, docosoic acid, tricosanic acid, Lignoceric acid, pentacosoic acid, hexacosanoic acid, carboceric acid, octocosoic acid, montanic acid, triacontanoic acid, myricinic acid, n-Dotriacontanoic acid, psyllic acid, gheddic acid, pentatriacontane acid, ceroplastic scid, heptatriacontane acid, octatriacontanoic acid, tetracontane acid, four hexadecanoic acids, pentacontane acid, hexacontane acid.

As the alkyl of straight chain, preferred carbonatoms is 20～30, and this can make the intermiscibility and/or the favorable dispersity of it and synthetic resins, and can make the ratio of the benzotriazole skeleton with ultraviolet radiation absorption function suitable.

The object lesson of above-mentioned preferred benzotriazole cpd can be enumerated following represented compound N o12～16.

The following describes that X is (b) and situation (c) in the triaizine compounds involved in the present invention.

In the case, R ' be carbonatoms be 5～60 alicyclic radical or endways or the alkane 2 basis, the carbonatoms that have alicyclic radical in the chain be that 9～60 the alkane 2 basis with side chain, carbonatoms are the alkane 2 basis of 20～60 straight chain.Wherein, alicyclic radical or endways or have the alkane 2 basis of alicyclic radical in the chain, being more preferably carbonatoms is 5～19 preferably.

As X is (b) and the preferred form (c) time, and in the represented chain of R ' alicyclic radical being arranged or the carbonatoms of alicyclic radical is arranged is that 5～19 alkane 2 basis can be enumerated the represented group of following general formula (4).

In the formula, A, Ra are identical with above general formula (1) with 9 for ring, and Rc and Rd represent alkane 2 basis, and q, r represent 0 or 1, and the former number of the carbon of whole group adds up to 5～19.

Above-mentioned R ' derives out from organic dicarboxylic acid with alicyclic radical or acid anhydrides.This organic carboxyl acid can be enumerated: 1, and 2-encircles pentane dicarboxylic acid, 1, and 3-encircles pentane dicarboxylic acid, 1,2-cyclohexyl dicarboxylic acid, 1,3-cyclohexyl dicarboxylic acid, 1,4-cyclohexyl dicarboxylic acid, 1,4-dicarboxyl methylene radical hexanaphthene etc.; Described acid anhydrides can be enumerated: methyl tetrahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, 4-norbornylene-1,2-dicarboxylic anhydride, methyl 4-norbornylene-1,2-dicarboxylic anhydride, trialkyl Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride etc.

O.17-22 X can enumerate the following stated compound N for the object lesson of the triaizine compounds of (b).

When the X in the above general formula (I) is (c), R ²For be selected from carbonatoms be 1～18 have a side chain or endways or have the alkyl of alicyclic radical and the group (carbon atom comprises alicyclic radical) of (many) alkoxyalkyls in the chain.

Carbonatoms be 1～18 have side chain endways or the alkyl that has alicyclic radical in the chain can enumerate: methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, isobutyl-, amyl group, isopentyl, tert-pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, the 2-heptyl, the 3-heptyl, different heptyl, uncle's heptyl, amyl group, tert-pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, the 2-heptyl, the 3-heptyl, different heptyl, uncle's heptyl, n-octyl, iso-octyl, uncle's octyl group, the 2-ethylhexyl, nonyl, different nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl etc.

Carbonatoms is that (many) alkoxyalkyls of 1～18 can be enumerated: methoxy ethyl, ethoxyl methyl, propoxy-ethyl, butoxyethyl group, 2-(2-methoxy ethoxy) ethyl, 2-(2-butoxy oxyethyl group) ethyl, 2-[2-(2-methoxy ethoxy) oxyethyl group] ethyl etc.

X is that o.23～28 the object lesson of the triaizine compounds of (c) can enumerate the following stated compound N.

The following describes that X is the situation of (d) in the triaizine compounds involved in the present invention.

In the case, R ' be carbonatoms be 5～60 alicyclic radical or endways or the alkane 2 basis, the carbonatoms that have alicyclic radical in the chain be that 9～60 the alkane 2 basis that side chain is arranged, carbonatoms are 20～60 straight chain alkane 2 basis.

Derive out from corresponding organic dicarboxylic acid, dicarboxylic anhydride with the alkane 2 basis that R ' represents, can introduce alicyclic radical or endways or the carbonatoms that has the alkane 2 basis of alicyclic radical in the chain be that 5～60 dicarboxylic acid can be enumerated: 1,2-encircles pentane dicarboxylic acid, 1,3-encircles pentane dicarboxylic acid, 1,2-cyclohexyl dicarboxylic acid, 1,3-cyclohexyl dicarboxylic acid, 1,4-cyclohexyl dicarboxylic acid, 1,4-dicarboxyl methylene radical hexanaphthene, dimeracid, hydrogenated dimer acids etc.; Acid anhydrides can be enumerated: methyl tetrahydrophthalic anhydride, Tetra Hydro Phthalic Anhydride, 4-norbornylene-1,2-dicarboxylic anhydride, methyl 4-norbornylene-1,2-dicarboxylic anhydride, trialkyl Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride etc.

Introducing has the dicarboxylic acid of the alkane 2 basis of side chain can enumerate 8,13-dimethyl-1-, 18-18 methylene radical dicarboxylic acid etc.; Introduce the dicarboxylic acid of the alkane 2 basis of straight chain and can enumerate 1-, 20-two decamethylene dicarboxylic acid, 1-, 20-21 methylene radical dicarboxylic acid, 1-, 22-20 dimethylene dicarboxylic acid, 1-, 24-20 tetramethylene dicarboxylic acid, 1-, 28-28 methylene radical dicarboxylic acid, 1-, 32-30 dimethylene dicarboxylic acid etc.

Above-mentioned these with the R ' in the group of (d) expression, preferably carbonatoms is 5～60 a alicyclic radical or endways or have the alkane 2 basis of alicyclic radical in the chain.The compound N that object lesson with triaizine compounds of these preferred R ' can be enumerated the following stated o.29～43.

In the above general formula (I) involved in the present invention, the represented carbonatoms of R is 1～4 alkyl, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, isobutyl-etc.

And in the above general formula (I), n can make being colored as of compound resin composition minimum at 0 o'clock, therefore better.

The represented triaizine compounds of above general formula (I) involved in the present invention, its manufacture method is not particularly limited, available well-known common method for making.

At X is when using the group of (a) expression, for example, can pass through 2-[2-hydroxyl-4-(2-hydroxyethyl oxygen) phenyl]-4,6-phenylbenzene-1,3, the esterification or the transesterification reaction of the derivative compound of the ester of 5-pyrrolotriazine derivatives and corresponding aliphatic carboxylic acid (aliphatic carboxylic acid, aliphatic carboxylic acid halogenide or aliphatic carboxylic acid esters) make.

At X is when using the group of (b) expression, for example, can pass through 2-[2-hydroxyl-4-(2-hydroxyethyl oxygen) phenyl]-4,6-phenylbenzene-1,3, the esterification or the transesterification reaction of the derivative compound of the ester of 5-pyrrolotriazine derivatives and corresponding organic dicarboxylic acid (monoesters of organic dicarboxylic acid, organic dicarboxylic acid-halogenide or organic dicarboxylic acid) make.

At X is when using the group of (c) expression, for example, can be the esterification of using the compound of (b) expression by corresponding alkylol cpd and X, 2-[2-hydroxyl-4-(2-hydroxyethyl oxygen) phenyl]-4,6-phenylbenzene-1,3,5-pyrrolotriazine derivatives and the corresponding derivative compound of ester (organic dicarboxylic acid monoesters, organic dicarboxylic acid monoesters-halogenide, or organic dicarboxylic acid dibasic acid esters) esterification or transesterification reaction, corresponding alcohol and 2-[2-hydroxyl-4-(hydroxyethyl oxygen) phenyl]-4,6-phenylbenzene-1,3, the alkoxide component of 5-pyrrolotriazine derivatives and the corresponding derivative compound (organic dicarboxylic acid of organic dicarboxylic acid ester, the organic diacid acid ihalide, the organic dicarboxylic acid diester, acid anhydrides) esterification or transesterification reaction make.

At X is when using the group of (d) expression, for example, can pass through 2-[2-hydroxyl-4-(2-hydroxyethyl oxygen) phenyl]-4,6-phenylbenzene-1,3, the esterification or the transesterification reaction of the ester derivative compound (organic dicarboxylic acid, organic dicarboxylic acid dihalide, organic dicarboxylic acid diester, acid anhydrides) of 5-pyrrolotriazine derivatives and corresponding organic dicarboxylic acid make.

The compound resin composition that has comprised the UV light absorber of the triaizine compounds that comprises that aforementioned formula of the present invention (I) is represented, its used synthetic resins can be enumerated: alpha-olefinic polymer or D polyolefin resin and multipolymers thereof such as vinyl-vinyl acetate copolymer, ethylene/propene block or random copolymers such as new LDPE (film grade), straight chain shape new LDPE (film grade), high density polyethylene(HDPE), polypropylene, poly-1-butylene, poly-3-methyl butene, poly-4-methylpentene; The terpolymer of polyvinyl chloride, polyvinylidene dichloride, chlorinatedpolyethylene, poly(vinylidene fluoride), chlorinated rubber, vinyl chloride vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinylchlorid-vinylidene chloride-vinyl-acetic ester, vinyl chloride-acrylate copolymer, vinylchlorid-maleate copolymer, vinylchlorid-Halogen resins such as toxilic acid cyclohexyl multipolymer; Polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly terephthalic acid hexylene glycol ester; Polystyrene, high-impact polystyrene (HIPS), acrylonitrile-butadiene-styrene (ABS) (ABS), chlorinatedpolyethylene-acrylonitrile-styrene (ACS), styrene-acrylonitrile (SAN), vinyl cyanide-BA-St (AAS), butadiene-styrene, styrene-maleic acid, vinylbenzene-maleimide, ethylene-propylene-acrylonitrile-styrene (AES), divinyl-methyl methacrylate-vinylbenzene styrene resins such as (MBS); Polycarbonate resin such as polycarbonate, branched polycarbonate; Use the polyamide-based resin of aromatic dicarboxylic acid such as polyhexamethylene adipamide (nylon 66), polycaprolactam (nylon 6), nylon 6T or alicyclic dicarboxylic acid's polymeric amide etc.; Polymer alloy (polymeralloy), the LCP of polyphenylene oxide (PPO) resin, modified polyphenylene ether resin, polyphenylene sulfide (PPS) resin, polyoxymethylene (POM), modified polyacetal, petroleum resin, coumarone resin, vinylite, acrylic resin, polycarbonate and styrene resin; Silicone resin; Urethane resin; Aliphatic dicarboxylic acid, aliphatic diol, aliphatic hydroxyl carboxylic acid or the aliphatic polyester of being derived out by their ring compound and they make biodegradability resins such as polyester after molecular weight increases with vulcabond etc.; Cellulose-based resin; And their regenerating resin etc.

In compound resin composition of the present invention, comprise the optional arbitrary value of incorporation of the UV light absorber of triaizine compounds, be not particularly limited.Its incorporation is with respect to 100 mass parts synthetic resins, preferably 0.001～25 mass parts, more preferably 0.01～15 mass parts, as less than 0.001 mass parts, then can not get effect, as surpassing 25 mass parts, then additive effect is not only carried not highly, and causes cost to rise.

In compound resin composition of the present invention, be the additives such as antioxidant of photostabilizer, phenol system, sulphur system, phosphorus system for making its more stabilization, can adding hindered amine in case of necessity.In addition, also can be used in combination with the UV light absorber except the represented compound of aforementioned formula of the present invention (I).

Especially hindered amine is photostabilizer (below be sometimes referred to as HALS), have with molecule in the functional group of a nitrogen atomic linkage of N-proton, N--oxyl, N-alkoxyl group, N-alkyl, N-hydroxyl etc., seizure by resin because of ultraviolet ray, light or the thermogenetic oxidizable compounds that decomposes in free radical and the resin combination, thereby resin and resin combination thereof have been given with weather resistant functions, itself and UV light absorber be used in combination reach the multiplication effect, therefore, be specially adapted to polyolefin resin.

Above-mentioned HALS can enumerate the represented compound of following general formula (II), cyanuryl chloride condensed type, high molecular type etc.

In the formula; m is 1～6 integer; A be hydrogen atom, carbonatoms be 1～18 m valency alkyl, m valency acyl group or m valency formamyl, B be Sauerstoffatom ,-NH-or have carbonatoms be 1～8 alkyl Re-NRe-; Y is that hydrogen atom, oxyradical (O), carbonatoms are that 1～18 alkoxyl group, carbonatoms are 1～8 alkyl, hydroxyl, and Z is methyne or has the following represented group (III) that carbonatoms is 1～8 alkyl Rf.

In above general formula (II), the m valency carbonatoms of representing with A is 1～18 alkyl, can enumerate the group (alkyl, alkane 2 basis or alkane six bases) of being derived out by following alkane: methane, ethane, propane, butane, secondary butane, uncle's butane, different propane, pentane, iso-pentane, uncle's pentane, hexane, hexanaphthene, heptane, isoheptane, uncle's heptane, octane, octane-iso, uncle's octane, 2-ethyl hexane, nonane, isononane, decane, dodecane, tridecane, the tetradecane, pentadecane, n-Hexadecane, heptadecane, octadecane etc.

M valency acyl group among the above-mentioned A is the (group that the alkane ester (they are called the acyl group derivative compound) of n～m) derives out by the n divalent carboxylic acid of carboxylic acid, m divalent carboxylic acid and a residual m carboxyl.

Described acyl group derivative compound can be enumerated: acetate; phenylformic acid; the 4-trifluoromethylbenzoic acid; Whitfield's ointment; vinylformic acid; methacrylic acid; oxalic acid; propanedioic acid; succsinic acid; pentanedioic acid; hexanodioic acid; pimelic acid; suberic acid; nonane diacid; sebacic acid; the dodecyl diacid; the 2-methylsuccinic acid; 2-methyl hexanodioic acid; 3-methyl hexanodioic acid; the 3-methylglutaric acid; 2-methyl suberic acid; 3; 8-dimethyl sebacic acid; 3; 7-dimethyl sebacic acid; hydrogenated dimer acids; dimeracid; phthalic acid; terephthalic acid; m-phthalic acid; naphthalic acid; cyclohexane dicarboxylic acid; trimellitic acid; trimesic acid; propane-1; 2; the 3-tricarboxylic acid; propane-1; 2; 3 tricarboxylic acid list or dialkyls; pentane-1,3, the 5-tricarboxylic acid; pentane-1; 3; 5-tricarboxylic acid list or dialkyl; butane-1,2,3; the 4-tetracarboxylic acid; butane-1; 2,3,4-tetracarboxylic acid list or three alkane esters; pentane-1; 2; 3,4, the 5-pentacarboxylic acid; pentane-1; 2; 3,4,5-pentacarboxylic acid list or four alkane esters; hexane-1; 2; 3,4,5; the 6-hexacarboxylic acid; hexane-1; 2,3,4; 5,6-hexacarboxylic acid list or five alkane esters etc.

M valency formamyl is an alkyl-carbamoyl or the dialkyl amido formyl radical of being derived out by isocyanate compound among the above-mentioned A.The isocyanic ester that derives an alkyl-carbamoyl can be enumerated: tolylene diisocyanate; ditan-4; 4 '-vulcabond; PPDI; Xylene Diisocyanate; 1; the 5-naphthalene diisocyanate; 3; 3 '-dimethyl diphenyl-4; 4 '-vulcabond; dianisidine diisocyanate; tetramethyl xylylene diisocyanate; isophorone diisocyanate; dicyclohexyl methyl hydride-4; 4 '-vulcabond; anti-form-1; the 4-cyclohexyl diisocyanate; the norbornylene vulcabond; 1; hexamethylene-diisocyanate; 2; 2; 4 (2; 2; 4)-the trimethylammonium hexamethylene diisocyanate; lysinediisocyanate; triphenylmethane triisocyanate; 1-methylbenzene-2,4, the 6-triisocyanate; dimethyl triphenyl methane tetraisocyanate etc.The dialkyl amido formyl radical can be enumerated: diethylamino formyl radical, dibutylamino formyl radical, dihexyl formamyl, dioctyl formamyl etc.

The above-mentioned group that these are represented with A can be by replacements such as halogen atom, hydroxyl, alkyl, alkoxyl group, nitro, cyano group.

The carbonatoms of representing with Re that is replaced by N in the B of formula (II) is that 1～8 alkyl can be enumerated: methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, the tertiary butyl, different very little base, amyl group, isopentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, different heptyl, uncle's heptyl, 1-ethyl pentyl group, n-octyl, iso-octyl, uncle's octyl group, 2-ethylhexyl.

Y in the formula (II) represents that hydrogen atom, oxyradical (O), carbonatoms are that 1～18 alkoxyl group, carbonatoms are 1～8 alkyl or hydroxyl.

Above-mentioned carbonatoms is that 1～18 alkoxyl group can be enumerated: methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, sec-butoxy, tert.-butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy, the ninth of the ten Heavenly Stems oxygen base, different ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, dodecyloxy, tridecane oxygen base, tetradecyloxyaniline, pentadecane oxygen base, n-Hexadecane oxygen base, heptadecane oxygen base, octadecane oxygen base.Carbonatoms is that 1～8 alkyl can be enumerated the group identical with Re.

The carbonatoms of representing with Rf in the Z of formula (II) is that 1～8 alkyl can be enumerated the group identical as Re.

More specifically example with the HALS of above-mentioned general formula (II) expression can be enumerated: stearic acid (2,2,6,6-tetramethyl--4-piperidyl) ester, stearic acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester, phenylformic acid (2,2,6,6-tetramethyl--4-piperidyl) ester, sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester, sebacic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) ester, sebacic acid two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) ester, methacrylic acid (1,2,2,6,6-pentamethyl--4-piperidyl) ester, methacrylic acid (2,2,6,6-pentamethyl--piperidyl) ester, four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters, four (1,2,2,6,6-pentamethyl--4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters, two (2,2,6,6-tetramethyl--4-piperidyl) two (tridecyl)-1,2,3,4-butane tetracarboxylic acid esters, two (1,2,2,6,6-pentamethyl--4-piperidyl) two (tridecyl)-1,2,3,4-butane tetracarboxylic acid esters, propanedioic acid two (1,2,2,6,6-pentamethyl--4-piperidyl)-2-butyl-2-(3,5-di-t-butyl-4-acrinyl) ester, 3,9-two [1,1-dimethyl-2-{ three (2,2,6,6-tetramethyl--4-piperidyl oxygen ketonic oxygen) butyl ketonic oxygen } ethyl]-2,4,8,10-Si Evil spiral shell [5,5] undecane, 3,9-two [1,1-dimethyl-2-{ three (1,2,2,6,6-pentamethyl--4-piperidyl oxygen ketonic oxygen) the butyl ketonic oxygen } ethyl]-2,4,8,10-Si Evil spiral shell [5,5] undecane etc.

Cyanuryl chloride condensed type HALS can enumerate: 1.6-two [2,2,6,6-tetramethyl--4-piperidyl amino] hexane/2,4-two chloro-6-morpholinoes-5-triazine polycondensate, 1,6-two (2,2,6,6-tetramethyl--4-piperidyl amino) hexane/2,4-two chloro-uncle 6-octyl group amino-2-triazine polycondensates, 1,5,8, and 12-four [2,4-two (N-butyl-N-(2,2,6,6-tetramethyl--4-piperidyl) amino)-s-(6-triazinyl)]-1,5,8,12-four aza-dodecanes, 1,5,8,12-four [2, (N-butyl-N-(1,2,2 for 4-two, 6,6-pentamethyl--4-piperidyl) amino)-s-(6-triazinyl)]-1,5,8,12-four aza-dodecanes, 1,6,11-three [2,4-two (N-butyl-N-(2,2,6,6-tetramethyl--4-piperidyl) amino)-s-(6-triazinyl) amino] undecane, 1,6,11-three [2,4-two (N-butyl-N-(1,2,2,6,6-pentamethyl--4-piperidyl) amino)-s-(6-triazinyl) amino] undecane etc.

Enumerating of high molecular type: 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl--4-piperidines alcohol (piperidinol)/ethyl succinate polycondensate, 1,6-two (2,2,6,6-tetramethyl--4-piperidyl amino) hexane/ethylene dibromide polycondensate etc.

Above-mentioned HALS can also can be used in combination more than two kinds in a kind of use, its total incorporation is with respect to 100 mass parts thermoplastic resins, be preferably 0.001～10 mass parts, be more preferred from 0.01～2 mass parts, if be lower than 0.001 mass parts, then can not get effect, if surpass 10 weight parts, not only can not improve additive effect, and cause cost to rise.

Above-mentioned phosphorous antioxidant can be enumerated: triphenyl phosphite, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphite (2, the 5-di-tert-butyl-phenyl) ester, tricresyl phosphite (nonyl phenyl) ester, tricresyl phosphite (dinonyl phenyl) ester, tricresyl phosphite is (single, two mixed base nonyl phenyls) ester, acid phosphorous acid diphenyl ester, phosphorous acid [2,2 '-methylene radical two (4, the 6-di-tert-butyl-phenyl) octyl group] ester, phosphorous acid phenylbenzene ester in the last of the ten Heavenly stems, phosphorous acid phenylbenzene monooctyl ester, diphosphorous acid two (nonyl phenyl) pentaerythritol ester, phosphorous acid phenyl two isodecyl esters, tributyl phosphate, tricresyl phosphite (2-ethylhexyl) ester, tridecyl phosphite, trilauryl phosphite, the acid dibutyl phosphite, acid phosphorous acid two lauryls, trilauryl trithiophosphite, two (neopentyl glycol) 1,4-hexanaphthene dimethyl diphosphites, diphosphorous acid two (2, the 4-di-tert-butyl-phenyl) pentaerythritol ester, diphosphorous acid two (2, the 5-di-tert-butyl-phenyl) pentaerythritol ester, diphosphorous acid two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol ester, diphosphorous acid two (2, the 4-dicumylphenyl) pentaerythritol ester, diphosphorous acid distearyl pentaerythritol ester, phosphorous acid [four (C12-15 mixed alkyls)-4,4 '-the isopropylidene phenylbenzene] ester, two [2,2 '-methylene radical two (4,6-diamyl phenyl)] isopropylidene phenylbenzene phosphorous acid ester, four (tridecyls) 4,4 '-butylidene two (the 2-tertiary butyl-5-methylphenol) diphosphites, six (tridecyls) 1,1,3-three (the 2-methyl-5-tertiary butyl-4-hydroxyphenyl) butane GW-540, diphosphorous acid [four (2, the 4-di-tert-butyl-phenyl) diphenylene] ester, three (2-[(2,4,7,9-tetra-tert dibenzo [d, f] [1,3,2] Er Evil (6-phosphniline product (phosphepin) base) oxygen] ethyl) amine, 9,10-dihydro-9-Evil-10-phospho hetero phenanthrene-10-oxide compound, 2-butyl-2-ethyl glycol 2,4,6-tri-butyl-phenol-phosphorous acid ester etc.

Above-mentioned phenol is that polyphenoils can be enumerated: 2,6-di-t-butyl-p-cresol, 2,6-phenylbenzene-4-octadecane oxygen base phenol, propionic acid [stearyl (3,5-di-t-butyl-4-hydroxyphenyl)] ester, phosphonic acids propionic acid distearyl (3,5-di-t-butyl-4-acrinyl) ester, tridecyl 3,5-di-t-butyl-4-acrinyl thioacetate, sulfo-diethylidene two [propionic acid (3,5-di-t-butyl-4-hydroxyphenyl) ester], 4,4 '-sulfo-two (the 6-tertiary butyl-meta-cresol), 2-octylsulfo-4,6-two (3,5-di-t-butyl-4-hydroxyphenoxy)-the s-triazine, 2,2 '-methylene radical two (4-methyl-6-tert butyl phenol), two [3,3-two (4-hydroxyl-3-tert-butyl-phenyl) butyric acid] glycol ester, 4,4 '-butylidene two (2, the 6-DI-tert-butylphenol compounds), 4,4 '-butylidene two (the 6-tertiary butyl-3-methylphenol), 2,2 '-ethylene (4, the 6-DI-tert-butylphenol compounds), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, terephthalic acid two [the 2-tertiary butyl-4-methyl-6-(the 2-hydroxyl-3-tertiary butyl-5-methyl-benzyl) phenyl] ester, tricarbimide [1,3,5-three (2,6-dimethyl-3-hydroxyl-4-tertiary butyl benzyl)] ester, tricarbimide [1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)] ester, 1,3,5-three (3,5-di-t-butyl-4-acrinyl)-2,4, the 6-Three methyl Benzene, tricarbimide { 1,3,5-three [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy ethyl] } ester, four [methylene radical-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] methane, the 2-tertiary butyl-4-methyl-6-(the 2-acryloxy-3-tertiary butyl-5-methyl-benzyl) phenol, 3,9-two [2-(3-tertiary butyl-4-hydroxy-5-hydrogenated methyl cinnamoyloxy group)-1, the 1-dimethyl ethyl foretells 2,4,8,10-Si Evil spiral shell [5,5] undecane, two [β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic acid] triethyleneglycol ester etc.

Above-mentioned sulphur is that antioxidant can be enumerated: the thio-2 acid dialkyl class of the lauryl of thio-2 acid, two myristins, myristyl stearyl, distearyl ester etc., and the β-alkyl thiol propionic acid ester of the polyvalent alcohol of four (β-dodecyl thiohydracrylic acid) pentaerythritol ester etc.

Above-mentioned UV light absorber can be enumerated: 2,4 dihydroxyl benzophenone, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-octyloxy benzophenone, 5,5 '-the 2-hydroxy benzophenone ketone of methylene radical two (2-hydroxyl-4-methoxy benzophenone) etc.; 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, 2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 5-chlorinated benzotriazole, 2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-5-chlorinated benzotriazole, 2-(2-hydroxyl-3, the 5-dicumylphenyl) benzotriazole, 2,2 '-methylene radical two (uncle's 4-octyl group-6-benzotriazole base phenol), the macrogol ester of 2-(the 2-hydroxyl-3-tertiary butyl-5-carboxyl phenyl) benzotriazole, 2-[2-hydroxyl-3-(2-acryloxy ethyl)-5-aminomethyl phenyl] benzotriazole, 2-[2-hydroxyl-3-(2-methacryloxyethyl)-5-tert-butyl-phenyl] benzotriazole, 2-[2-hydroxyl-3-(2-methacryloxyethyl)-uncle's 5-octyl phenyl] benzotriazole, 2-[2-hydroxyl-3-(2-methacryloxyethyl)-5-tert-butyl-phenyl]-the 5-chlorobenzotriazole, 2-[2-hydroxyl-5-(2-methacryloxyethyl) phenyl] benzotriazole, 2-[2-hydroxyl-3-the tertiary butyl-5-(2-methacryloxyethyl) phenyl] benzotriazole, 2-[2-hydroxyl-3-tert-pentyl-5-(2-methacryloxyethyl) phenyl] benzotriazole, 2-[2-hydroxyl-3-the tertiary butyl-5-(3-methacryloxypropyl) phenyl]-the 5-chlorobenzotriazole, 2-2[hydroxyl-3-the tertiary butyl-5-(3-methacryloxypropyl) phenyl]-the 5-chlorobenzotriazole, 2-[2-hydroxyl-4-(2-methacryloxy methyl) phenyl] benzotriazole, 2-[2-hydroxyl-4-(3-methacryloxy-2-hydroxypropyl) phenyl] benzotriazole, 2-[2-hydroxyl-4-(3-methacryloxypropyl) phenyl] 2-(2-hydroxyphenyl) benzotriazole category of benzotriazole etc.; Salol, resorcinol monobenzoate, phenylformic acid (2,4-di-tert-butyl-phenyl-3,5-di-t-butyl-4-hydroxyl) benzoates such as ester, phenylformic acid (hexadecyl-3,5-di-t-butyl-4-hydroxyl) ester, phenylformic acid stearyl (3,5-di-t-butyl-4-hydroxyl) ester; 2-ethyl-2 '-oxyethyl group oxanilide, 2-oxyethyl group-4 '-the replacement oxanilide class of dodecyl oxanilide etc.; Cyanoacrylates such as vinylformic acid (ethyl-alpha-cyano-β, β-phenylbenzene) ester, phenylformic acid [methyl-2-cyano group-3-methyl-3-(right-p-methoxy-phenyl)] ester; The salt of various metal-salts or metallo-chelate, particularly nickel or chromium or inner complex class.

The consumption of above-mentioned various additives with respect to 100 mass parts synthetic resins, is advisable with 0.001～20 mass parts, and 0.01～1 mass parts is better.As be lower than 0.001 mass parts, and then can not get effect sometimes, as surpassing 20 weight parts, then can not only can not improve additive effect, and cost rises.

In the compound resin composition of the present invention, can add in case of necessity: the heavy metal inert agents; Right-p t butylbenzoic acid aluminium; Dibenzylidene sorbitol; Metallic soap; Static inhibitor such as nonionic surface active agent, cationic surfactant, aniorfic surfactant, amphoterics; Fire retardants such as halogen (bromine, chlorine, fluorine) based compound, phosphorus series compound, metal oxide, fluoro-resin; Lubricants such as ethylene alkylamide; The tinting material of dyestuff, pigment etc.; The agent of crystallization such as nucleator, crystallization promoter; Processing aid; Well-known typical additives such as inorganic additivess such as hydrotalcite, talcum, mica, silica, weighting agent.

In the present invention, in thermoplastic resin, add with the represented UV light absorber of above general formula (I), and the addition means of other additive that adds in case of necessity, do not have specific limited, the form during interpolation can be powder, single component (one pack) particle, suspension, emulsion or solution.

The working method and the purposes of compound resin composition of the present invention are as follows, do not have specific limited, can use common working method, all use in any purposes.Working method can be enumerated: rolling processing, extrude processing, coextrusion processing, injection molding, inflation moulding, blow molding, press process, roll-in processing etc.Its purposes can be enumerated: automobile resin components such as collision bumper, dashboard, switchboard; Tame electrical article resin components such as refrigerator, washing machine, suction cleaner; Household supplies such as tableware, bucket, bath article; Resin for bonding parts such as connector; Groceries product such as toy; Storage tank classes etc. are preserved, are preserved with such moulding product such as containers; Building materials are used, style strip antiultraviolet film, agricultural film; Show and use the optics filter; And various sheet materials etc.

Embodiment

Below, by Production Example, embodiment and comparative example etc., the present invention is made more specific description.But the present invention is not subjected to any restriction of described these embodiment etc.

Synthesis example

Synthesizing of midbody compound

In reacting, 141 gram benzamidine hydrochlorides and 99.0 gram Resorcinol benzoic ethers are dissolved in the 580 gram ethanol, add methanol solution 175 grams of 28 quality % sodium methylates, under 78 ℃, remove methyl alcohol while stirring with flask.After stirring 20 hours under 78 ℃, be cooled to 5 ℃, the solid phase that leaching is separated out again.The solid phase of gained is clean with methyl alcohol and washing, makes 55.2 grams and is faint yellow crystalline intermediate 2-(2,4-three hydroxyphenyl)-4,6-phenylbenzene-1,3,5-triazines (yield 38%).

The 2-(2 that makes more than in the flask of reaction usefulness, adding, 4-three hydroxyphenyl)-4,6-phenylbenzene-1,3,5-triazine 51.0 grams, ethylene bromohyrin 284 grams, dimethyl formamide 255 grams, under 85 ℃, splash into 48 quality % aqueous sodium hydroxide solutions, 87.6 grams again, reacted 10 hours down in 85 ℃, after being cooled to 5 ℃, under the temperature below 5 ℃, splash into concentrated hydrochloric acid again, the pH 7～6 that neutralizes, the solid phase that leaching is separated out, through washing, dry, make midbody compound 2-[2-hydroxyl-4-(2-hydroxy ethoxy) phenyl of 46.2 grams] 4,6-phenylbenzene-1,3,5-triazines (yield 80%).

Production Example 1

O.1 synthetic of compound N

With in the flask, in the midbody compound that 7.94 grams make with above synthesis example, add hexahydrobenzoic acid 2.58 grams, dimethylbenzene 50 grams, tosic acid 0.10 gram in the reaction of crossing, refluxed 10 hours in 140 ℃ of dehydrations through nitrogen replacement.Washing is 7 until intrasystem pH value, and leaching solid phase after filtering adds methyl alcohol then, makes it to separate out crystallization, makes the coarse crystallization recrystallize that obtains after the leaching with dimethylbenzene/methyl alcohol (1/3) solvent, and the yield with 81% obtains faint yellow crystallization.Following analysis is carried out in prepared crystallization, confirm this crystallization be exactly target compound be compound N o.1.

1. infrared rays (IR) is analyzed (centimetre-1): 3440 (hydroxyls), 2925,2850 (cyclohexyl), 1725 (ester groups), 1535,1510 (triazinyls), 1165 (ethers).

2. ultimate analysis (quality %): carbon; 72.3 (72.3), hydrogen; 5.61 (5.65), nitrogen; 8.71 (8.73).Below, () interior representation theory value (as follows).

3. fusing point (below, except that indicating especially, all be meant the peak value that records by differential scanning calorimeter (DSC) analysis): 157 ℃.

Production Example 2

O.3 synthetic of compound N

With in the flask, in the midbody compound that 7.94 grams make with above synthesis example, add 3-hexanaphthene propionic acid 3.12 grams, dimethylbenzene 50 grams, tosic acid 0.10 gram in the reaction of crossing, refluxed 10 hours in 140 ℃ of dehydrations through nitrogen replacement.Washing is 7 until intrasystem pH value, and leaching solid phase after filtering adds methyl alcohol then, makes it to separate out crystallization, makes the coarse crystallization recrystallize that obtains after the leaching with dimethylbenzene/methyl alcohol (1/3) solvent, and the yield with 83% obtains faint yellow crystallization.Following analysis is carried out in crystallization to gained, confirm this crystallization be exactly target compound be compound N o.3.

1. IR analyzes (centimetre-1): 3435 (hydroxyls), 2920,2850 (cyclohexyl), 1728 (ester groups), 1535,1512 (triazinyls), 1165 (ethers).

2. ultimate analysis (quality %): carbon; 72.6 (72.7), hydrogen; 5.88 (5.90), nitrogen; 8.46 (8.48).

3. fusing point: 124 ℃.

Production Example 3

O.8 synthetic of compound N

With in the flask, in the midbody compound that 7.94 grams make with above synthesis example, add 2-hexyldecanoic acid 5.13 grams, dimethylbenzene 50 grams, tosic acid 0.10 gram in the reaction of crossing, refluxed 10 hours in 140 ℃ of dehydrations through nitrogen replacement.Washing is 7 until intrasystem pH value, and leaching solid phase after filtering adds methyl alcohol then, makes it to separate out crystallization, makes the coarse crystallization recrystallize that obtains after the leaching with dimethylbenzene/methyl alcohol (1/3) solvent, and the yield with 96% obtains faint yellow crystallization.Following analysis is carried out in crystallization to gained, confirm this crystallization be exactly target compound be compound N o.8.

1. IR analyzes (centimetre-1): 3437 (hydroxyls), 2924,2855 (alkyl), 1728 (alkyl), 1535,1510 (triazinyls), 1165 (ethers).

2. ultimate analysis (quality %): carbon; 75.0 (75.09), hydrogen; 7.90 (7.92), nitrogen; 6.71 (6.74).

3. fusing point: 80 ℃.

Production Example 4

O.9 synthetic of compound N

With in the flask, in the midbody compound that 7.94 grams make with above synthesis example, add 2-(1 in the reaction of crossing through nitrogen replacement, 3,3-trimethylammonium butyl)-5,7, sad 5.70 grams of 7-trimethylammonium, dimethylbenzene 50 grams, tosic acid 0.10 gram refluxed 10 hours in 140 ℃ of dehydrations.Washing is 7 until intrasystem pH value, leaching solid phase after filtering, and then, desolventizing makes the residue recrystallize of gained with dimethylbenzene/methyl alcohol (1/10) solvent, and the yield with 94% obtains faint yellow crystallization.Following analysis is carried out in crystallization to gained, confirm this crystallization be exactly target compound be compound N o.9.

1. IR analyzes (centimetre-1): 3444 (hydroxyls), 2955,2905,2866 (alkyl), 1732 (fat base), 1535,1512 (triazinyls), 1165 (ethers).

2. ultimate analysis (quality %): carbon; 75.5 (75.54), hydrogen; 8.20 (8.19), nitrogen; 6.44 (6.45).

3. fusing point: 71 ℃.

Production Example 5

O.11 synthetic of compound N

With in the flask, in the midbody compound that 7.94 grams make with above synthesis example, add 2-octyl group dodecylic acid 6.25 grams, dimethylbenzene 50.0 grams, tosic acid 0.10 gram in the reaction of crossing, refluxed 10 hours in 140 ℃ of dehydrations through nitrogen replacement.Washing is 7 until intrasystem pH value, leaching solid phase after filtering, and then, desolventizing, the residue of gained are with 40～50 ℃ methanol wash secondary, and by decantation, the yield with 92% obtains faint yellow solid again.Prepared solid is carried out following analysis, confirm this solid be exactly target compound be compound N o.11.

1. IR analyzes (centimetre-1): 3444 (hydroxyls), 2958,2928,2870 (alkyl), 1723 (ester groups), 1537,1515 (triazinyls), 1175 (ethers).

2. ultimate analysis (quality %): carbon; 76.0 (75.96), hydrogen: 8.42 (8.45), nitrogen; 6.16 (6.18)

3. fusing point: 57 ℃.

Production Example 6

O.12 synthetic of compound N

In the flask of reaction usefulness, in the midbody compound that 15.0 grams make with above synthesis example, add docosoic acid 16.0 grams, dimethylbenzene 45.0 grams, tosic acid 0.60 gram, refluxed 10 hours in 140 ℃.Add methyl alcohol to washing the back in the system, make it to separate out crystallization, make the coarse crystallization recrystallize that obtains after the leaching, obtain faint yellow crystallization 22.0 grams (yield 80%) with dimethylbenzene/methyl alcohol (1/3) solvent.Following analysis is carried out in prepared crystallization, confirm this crystallization be exactly target compound be compound N o.12.

1. IR analyzes (centimetre-1): 3440 (hydroxyls), 2920,2845 (chain alkyls), 1750 (ester groups), 1160 (ethers).

2. ultimate analysis (quality %): carbon; 76.4 (76.3), hydrogen; 8.7 (8.68), nitrogen; 5.9 (5.94).

3. fusing point: 113 ℃.

Production Example 7

O.29 synthetic of compound N

Use in the flask through the reaction that nitrogen replacement is crossed, in the midbody compound that 8.68 grams make with above synthesis example, adding 4-cyclohexane dicarboxylic acid 1.9 grams, dimethylbenzene 50.0 grams, tosic acid 0.10 restrain, and reflux 10 hours in 140 ℃.Cool to room temperature makes that the solid of gained is dissolved in tetrahydrofuran (THF) after the leaching, forms solution, adds methyl alcohol then, makes it to separate out crystallization, and the yield with 62% obtains little yellow crystal.Following analysis is carried out in prepared crystallization, confirm this crystallization be exactly target compound be compound N o.29.

1. IR analyzes (centimetre-1): 3440 (hydroxyls), 2940,2870 (cyclohexyl), 1723 (ester groups), 1537,1515 (triazinyls), 1175 (ethers).

2. ultimate analysis (quality %): carbon; 71.0 (71.1), hydrogen; 4.80 (4.82), nitrogen; 9.54 (9.56).

3. fusing point test (visual): 213～215 ℃.

Production Example 8

O.32 synthetic of compound N

With in the flask, in the midbody compound that 8.68 grams make with above synthesis example, add 1 in the reaction of crossing through nitrogen replacement, 2-cyclohexane dicarboxylic acid 1.9 grams, dimethylbenzene 50.0 grams, tosic acid 0.10 gram refluxed 10 hours in 140 ℃ of dehydrations.Washing is 7 until intrasystem pH value, and leaching solid phase after filtering adds methyl alcohol then, makes it to separate out crystallization, makes the coarse crystallization recrystallize that obtains after the leaching with dimethylbenzene/methyl alcohol (1/3) solvent, and the yield with 50% obtains faint yellow crystallization.Following analysis is carried out in prepared crystallization, confirm this crystallization be exactly target compound be compound N o.32.

1. IR analyzes (centimetre-1): 3437 (hydroxyls), 2943,2858 (cyclohexyl), 1743 (ester groups), 1531,1510 (triazinyls), 1173 (ethers).

2. ultimate analysis (quality %): carbon; 71.0 (71.1), hydrogen; 4.80 (4.82), nitrogen; 9.54 (9.56).

3. fusing point; 204 ℃.

Production Example 9

O.42 synthetic of compound N

In the flask of reaction usefulness, in the midbody compound that 15.0 grams make with above synthesis example, add hydrogenated dimer acids 11.0 grams, dimethylbenzene 45.0 grams, tosic acid 0.60 gram, refluxed 10 hours in 140 ℃.Add methyl alcohol to washing the back in the system, make it to separate out crystallization, make the coarse crystallization recrystallize that obtains after the leaching with dimethylbenzene/methyl alcohol (1/3) solvent, the yield with 93% obtains the faint yellow crystallization of 23.3 grams.Following analysis is carried out in prepared crystallization, confirm this crystallization be exactly target compound be compound N o.42.

1. IR analyzes (centimetre-1): 3440 (hydroxyls), 2920,2850 (alkyl), 1740 (ester groups), 1160 (ethers).

2. ultimate analysis (quality %): carbon; 76.0 (75.8), hydrogen; 7.9 (7.91), nitrogen; 6.4 (6.47).

3. fusing point: 87 ℃.

Compare Production Example

The manufacturing of comparative compound 1～5

Make following comparative compound 1～5 according to the step identical by corresponding raw material with above-mentioned synthesis example and manufacturing embodiment.

Embodiment 1

Mixed 5 minutes according to following prescription 1 with mixing machine, obtain resin combination, under 280 ℃, it is extruded processing, obtain pellet with 80 rev/mins, the tectum resin combination that will make by this pellet with by bisphenol A polycarbonate (limiting viscosity 0.57; 30 ℃ of dioxs) the sandwich layer resin of powder formation carries out coextrusion more simultaneously under 280 ℃, and corresponding surface is in contact with one another, and makes to have 2 mm thick sandwich layers and the tectal double-deck test film of 50 micron thickness.Under the condition shown in each table marge, (Sunshine Weather-O-meter) carries out atmospheric exposure test to this test film with daylight atmospheric corrosion resistance trier.With yellow degree (YI) before the colorimeter evaluation test of Hunter (Hunter) and poor (the Δ Y) of yellow degree after atmospheric exposure test and YI.The results are shown in table 1～3.

(prescription 1) (unit: mass parts)

Bisphenol A polycarbonate 100 mass parts

(limiting viscosity 0.57; 30 ℃ of dioxs)

UV light absorber (listing in table 1～3) 10

Comparative example 1

According to making the test film that do not mix UV light absorber and, carry out the evaluation of gonorrhoea degree and weathering resistance with the test film of comparative compound as UV light absorber with embodiment 1 identical step.It the results are shown in table 1～3.

Table 1

????No.	UV light absorber	????YI	????ΔY
				Embodiment 1-3	Compound N o.1	????13.5	????4.9
Embodiment 1-4	Compound N o.3	????13.0	????4.5
				Embodiment 1-5	Compound N o.32	????13.2	????4.3
Comparative example 1-4	??-	????10.5	Albefaction
				Comparative example 1-5	Comparative compound 1	????14.8	????6.9
Comparative example 1-6	Comparative compound 2	????13.6	????6.2
				Comparative example 1-7	Comparative compound 3	????13.8	5.9 gonorrhoea

83 ℃ of black floor temperature (black panel temperature) are with 18 minutes rainfall cycle rainfall 1050 hours in 120 minutes.

Table 2

????No.	UV light absorber	???YI	????ΔY
				Embodiment 1-6	Compound N o.8	???13.4	????4.5
Embodiment 1-7	Compound N o.9	???13.3	????4.2
				Embodiment 1-8	Compound N o.11	???13.2	????3.9
Comparative example 1-8	??-	???10.8	Albefaction
				Comparative example 1-9	Comparative compound 4	???14.2	????6.9

Black floor temperature 83,1050 hours.

Table 3

????No.	UV light absorber	????YI	????ΔY
				Embodiment 1-1	Compound N o.12	????13.5	????5.4
Embodiment 1-2	Compound N o.42	????13.1	????5.0
				Comparative example 1-1	Comparative compound 1	????15.8	????7.1
Comparative example 1-2	??-	????10.8	Albefaction
				Comparative example 1-3	Comparative compound 4	????14.2	????6.4

83 ℃ of black floor ℃ temperature, internal recycle rainfall in 120 minutes 18 minutes totally 1200 hours.

Embodiment 2

Mixed 5 minutes according to following prescription 2 with mixing machine, obtain resin combination, with 25 rev/mins it is extruded processing under 250 ℃, obtain pellet, this pellet is made thick 3 millimeters test film through injection molding again under 250 ℃.Under 89 ℃ black floor temperature temperature, use xenon lamp atmospheric corrosion resistance trier (XenonWeather-O-meter) to this test film atmospheric exposure test.Poor (Δ Y) with the yellow degree (YI) before the colorimeter evaluation test of Hunter and yellow degree after atmospheric exposure test in 1500 hours and YI.And produce the disruptive time (weather-proof time).The results are shown in table 4～8.

Comparative example 2

According to making the test film that does not mix UV light absorber and HALS, the test film that does not mix UV light absorber respectively with embodiment 2 identical steps and with the test film of comparative compound as UV light absorber, carry out the weathering resistance evaluation identical, the results are shown in table 4～80 with embodiment 2.

(prescription 2) (unit: mass parts)

Ethylene/propylene alkene block copolymer 100 mass parts

(ethylene/propene=3/97, MI=10)

Calcium stearate 0.05

Propionic acid [stearyl (3,5-di-t-butyl-4-hydroxyphenyl)] ester 0.1

Tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester 0.05

HALS (with reference to following table 4～8) table 4～8

UV light absorber 0.25

In addition, the body index (MI) that melts of ethylene/propene copolymer is meant the numerical value (unit gram/10 minutes) that records under 230 ℃, 2.16 kilograms of conditions of loading.

Table 4

HALS: two (2,2,6,6-tetramethyl--4-piperidyl) sebate

????No.	HALS (mass parts)	UV light absorber	The weather-proof time (hour)	??ΔY
					Embodiment 2-1	????0.25	Compound N o.3	????3150	??4.7
Embodiment 2-2	????0.25	Compound N o.32	????3300	??4.4
					Comparative example 2-1	????-	??-	????＜400	??-
Comparative example 2-2	????0.25	??-	????1400	??10.2
					Comparative example 2-3	????0.25	Comparative compound 2	????2450	??8.6
Comparative example 2-4	????0.25	Comparative compound 3	????2800	??7.9

Table 5

HALS: four (1,2,2,6,6-pentamethyl--4-piperidyl)-1,2,3,4 ,-butane tetracarboxylic acid esters

????No.	HALS (mass parts)	UV light absorber	The weather-proof time (hour)	??ΔY
					Embodiment 2-3	????0.25	Compound N o.3	????3450	??4.6
Embodiment 2-4	????0.25	Compound N o.32	????3650	??4.2
					Comparative example 2-5	????-	??-	????＜400	??-
Comparative example 2-6	????0.25	??-	????1400	??10.0
					Comparative example 2-7	????0.25	Comparative compound 2	????2650	??8.5
Comparative example 2-8	????0.25	Comparative compound 3	????2800	??7.7

Table 6

HALS: two (1,2,2,6,6-pentamethyl--4-piperidyl) two (three decyls) butane tetracarboxylic acid esters

????No.	HALS (mass parts)	UV light absorber	The weather-proof time (hour)	???ΔY
					Embodiment 2-5	????0.25	Compound N o.3	????3400	???4.6
Embodiment 2-6	????0.25	Compound N o.32	????3650	???4.4
					Comparative example 2-9	????-	??-	????＜400	???-
Comparative example 2-10	????0.25	??-	????1500	???10.0
					Comparative example 2-11	????0.25	Comparative compound 2	????2700	???8.6
Comparative example 2-12	????0.25	Comparative compound 3	????2900	???7.9

Table 7

HALS: four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters

????No.	HALS (mass parts)	UV light absorber	The weather-proof time (hour)	??ΔY
					Embodiment 2-7	????0.25	Compound N o.3	????3400	??4.5
Embodiment 2-8	????0.25	Compound N o.32	????3550	??4.3
					Comparative example 2-13	????-	??-	????＜400	??-
Comparative example 2-14	????0.25	??-	????1550	??10.5
					Comparative example 2-15	????0.25	Comparative compound 2	????2750	??8.5
Comparative example 2-16	????0.25	Comparative compound 3	????2850	??8.0

Table 8

HALS:1,5,8,12-four [2,4-two (N-butyl-N-(2,2,6,6-tetramethyl--4-piperidyl) amino)-s-(6-triazinyl)]-1,5,8,12-four aza-dodecanes

????No.	HALS (mass parts)	UV light absorber	The weather-proof time (hour)	???ΔY
					Embodiment 2-9	????0.25	Compound N o.3	??3200	???4.9
Embodiment 2-10	????0.25	Compound N o.32	??3400	???4.7
					Comparative example 2-17	????-	??-	??＜400	???-
Comparative example 2-18	????0.25	??-	??1500	???11.1
					Comparative example 2-19	????0.25	Comparative compound 2	??2500	???8.8
Comparative example 2-20	????0.25	Comparative compound 3	??2600	???8.0

Embodiment 3

Mixed 5 minutes according to following prescription 3 with mixing machine, obtain resin combination, with 25 rev/mins it is extruded processing under 250 ℃, obtain pellet, this pellet is made thick 1 millimeter test film through injection molding again under 250 ℃.Carry out following evaluation.The results are shown in table 9.

1. mist degree (gonorrhoea degree) and all-optical transmittance (transparency):, measure 30 days test film is preserved in the processing back in the time of 60 ℃ mist degree and all-optical transmittance (unit: %) according to JIS K 7105.(in the table, the numerical value after the numerical value of → front and back is represented respectively to process the back and preserve.)

2. initial coloring: measure the yellow degree (YI) of processing the back test film with the Hunter colorimeter, estimate tint permanence with this.

3. bleed (bleed): observe in 60 ℃ of test films of preserving 30 down and have or not bleed.

Comparative example 3

According to the step identical with embodiment 3, make the test piece of not mixing prescription 3 middle-ultraviolet lamp absorption agents and with the test film of comparative compound as UV light absorber, carry out the evaluation identical with embodiment 3, the result is in table 9.

(prescription 3) (unit: mass parts)

Ethylene/propylene olefinic random copolymer 100 mass parts

(ethylene/propene=3/97, MI=10)

Calcium stearate 0.1

Four [methylene radical-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid 0.1

Ester] methane

Tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester 0.1

UV light absorber 0.5

Table 9

????No.	UV light absorber	Mist degree	The logical rate of penetrating	Initial coloration	Bleed
						Embodiment 3-1	Compound N o.8	?48.4→51.3	?97.1→91.0	????3.6	Do not have
Embodiment 3-2	Compound N o.9	?49.6→52.6	?92.2→92.0	????3.6	Do not have
						Embodiment 3-3	Compound N o.11	?47.1→51.0	?91.0→90.9	????3.4	Do not have
Comparative example 3-1	-	?42.3→45.3	?93.6→93.5	????3.2	Do not have
						Comparative example 3-2	Comparative compound 4	?56.1→59.0	?88.8→88.2	????4.7	Little
Comparative example 3-3	Comparative compound 5	?62.4→66.7	?81.2→79.4	????4.0	Have

Embodiment 4

Mixed 5 minutes according to following prescription 4 with mixing machine, obtain resin combination, with 25 rev/mins it is extruded processing under 250 ℃, obtain pellet, this pellet is made thick 1 millimeter test film through injection molding again under 250 ℃.Carry out following evaluation.The results are shown in table 10.

1. mist degree (gonorrhoea degree) and all-optical transmittance (transparency): according to measuring with embodiment 3 identical methods.

2. weather resisteant:, under 83 ℃ black floor temperature, carry out atmospheric exposure test with daylight atmospheric corrosion resistance trier.The yellow degree YI before the evaluation test and the difference Δ Y and the time till generation is broken (weather-proof time) of the yellow degree after 1050 hours.

Comparative example 4

According to the step identical with embodiment 4, make the test film that does not mix prescription 4 middle-ultraviolet lamp absorption agents, carry out the evaluation identical with embodiment 4.The results are shown in table 10.

(prescription 4) (unit: mass parts)

Ethylene/propylene olefinic random copolymer 100 mass parts

(ethylene/propene=3/37, MI=10)

Calcium stearate 0.1

Four [methylene radical-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid 0.1

Ester] methane

Tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester 0.1

UV light absorber; Compound N o.11 0.5

HALS????????????????????????????????????????0.2

Table 10

????No.	HALS (mass parts)	Mist degree	Transmissivity	The weather-proof time (hour)	??YI	??ΔY
							Embodiment 4-1	?ADEKA?STAB?LA-62 *1	?48.6→51.6	?90.2→89.9	??3100	??3.8	??2.6
Embodiment 4-2	?ADEK?STAB?LA-63 *2	?48.4→51.9	?90.4→90.2	??3100	??3.8	??2.8
							Embodiment 4-3	?CHINUBIN?994 *3	?48.8→52.4	?90.1→89.9	??3000	??3.6	??3.4
Comparative example 4-1	ADEKA STAB LA-62 (no UVA)	?47.6→51.5	?92.9→92.6	??1250	??3.6	??12.4
							Comparative example 4-2	ADEKA STAB LA-63 (no UVA)	?47.4→51.4	?92.9→92.8	??1300	??3.6	??12.3
Comparative example 4-3	CHINUBIN 944 (no UVA)	?47.9→52.0	?92.7→92.5	??1200	??3.6	??13.0

* 1: the Xu Dianhuagongyeshe system; Two (tridecyl)-1,2,3, two (1,2,2,6,6-pentamethyl--4-piperidyl), 4-butane tetracarboxylic acid esters.

* 2: chemical industry society system in the rising sun; 3, and 9-two [1,1-dimethyl-2-{ three (1,2,2,6,6-pentamethyl--4-piperidyl oxygen ketonic oxygen) butyl ketonic oxygen } ethyl]-2,4,8,10-Si Evil spiral shell [5,5] undecane.

* 3:Chiba Speciality Chemicals society system: 1,6-two (2,2,6,6-tetramethyl--4-piperidyl amino) hexane/2,4-two chloro-uncle 6-octyl group amino-5-triazine polycondensates

Embodiment 5

Mixed 5 minutes according to following prescription 5 with mixing machine, obtain resin combination, with 25 rev/mins it is extruded processing under 250 ℃, obtain pellet, this pellet is made thick 2 millimeters test film through injection molding again under 250 ℃.In the black floor temperature is under the condition of 18 minutes rainfall cycles in 83 ℃, 120 minutes, with daylight atmospheric corrosion resistance trier this test film is carried out atmospheric exposure test.Estimate according to the yellow degree after on-test to 500 hour, after 1500 hours that records by the Hunter colorimeter with until producing the disruptive time (weather-proof time).The results are shown in table 11～15.

(prescription 5) (unit: mass parts)

Ethylene/propene copolymer 100 mass parts

Calcium stearate 0.05

Stearyl (3,5-di-t-butyl-4-hydroxyphenyl) propionic ester 0.1

Tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester 0.05

HALS table 11～15

UV light absorber 0.3

Table 11

HALS: sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester

????No.	HALS (mass parts)	UV light absorber	The weather-proof time (hour)	Huang Du
						500 hours	1500 hours
				Embodiment 5-1	??0.3			Compound N o.12	??3300	????4.0	??6.9
Embodiment 5-2	??0.3	Compound N o.42	??3400			????3.8	??6.5
				Comparative example 5-1	??0.3			Comparative compound 1	??2400	????5.0	??13.4
Comparative example 5-2	??0	?-	??400			????13.0	Black
				Comparative example 5-3	??0.3			?-	??1500	????9.2	??17.1

Table 12

HALS: four (1,2,2,6,6-pentamethyl--4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters

????No.	HALS (mass parts)	UV light absorber	The weather-proof time (hour)	Huang Du
						500 hours	1500 hours
				Embodiment 5-3	????0.3			Compound N o.12	???3700	????3.8	????6.4
Embodiment 5-4	????0.3	Compound N o.42	???3800			????3.6	????6.1
				Comparative example 5-4	????0.3			Comparative compound 1	???2700	????4.7	????11.6
Comparative example 5-5	????0.3	-	???1700			????8.8	????16.5

Table 13

HALS: two (1,2,2,6,6-pentamethyl--4-piperidyl) two (tridecyl) butane tetracarboxylic acid esters

????No.	HALS (mass parts)	UV light absorber	The weather-proof time (hour)	Huang Du
						500 hours	1500 hours
				Embodiment 5-5	????0.3			Compound N o.12	???3700	????4.4	????6.8
Embodiment 5-6	????0.3	Compound N o.42	???3800			????4.2	????6.5
				Comparative example 5-6	????0.3			Comparative compound 1	???2500	????5.3	????13.1
Comparative example 5-7	????0.3	-	???1600			????9.6	????17.0

Table 14

HALS: four (2,2,6,6-tetramethyl--4-piperidyl)-1,2,3,4-butane tetracarboxylic acid esters

????No.	HALS (mass parts)	UV light absorber	The weather-proof time	Huang Du
						500 hours	1500 hours
				Embodiment 5-7	????0.3			Compound N o.12	????3700	????4.2	????6.6
Embodiment 5-8	????0.3	Compound N o.42	????3700			????4.0	????6.2
				Comparative example 5-8	????0.3			Comparative compound 1	????2600	????5.0	????11.9
Comparative example 5-9	????0.3	-	????1600			????9.2	????17.2

Table 15

HALS:1,5,8,12-four [2, and 4-two (N-butyl-N-(2,2,6,6-tetramethyl--4-piperidyl) amino-s-(6-triazinyl)]-1,5,8,12-four aza-dodecanes

????No.	HALS (mass parts)	UV light absorber	The weather-proof time	Huang Du
						500 hours	1500 hours
				Embodiment 5-9	????0.3			Compound N o.12	????3400	????4.3	????7.2
Embodiment 5-10	????0.3	Compound N o.42	????3600			????4.0	????7.0
				Comparative example 5-10	????0.3			Comparative compound 1	????2400	????4.9	????12.7
Comparative example 5-11	????0.3	-	????1500			????9.0	????17.4

Embodiment 6

Mixed 5 minutes according to following prescription 6 with mixing machine, obtain resin combination, with 25 rev/mins it is extruded processing under 250 ℃, obtain pellet, this pellet is made thick 2 millimeters test film through injection molding again under 250 ℃.In the black floor temperature is under the condition of 18 minutes rainfall cycles in 83 ℃, 120 minutes, with daylight atmospheric corrosion resistance trier this test film is carried out atmospheric exposure test.Estimate according to the yellow degree after on-test to 500 hour, after 1500 hours that records by the Hunter colorimeter with until producing the disruptive time.The results are shown in table 16.

(prescription 6) (unit: mass parts)

Polypropylene 100 mass parts

(PROFAX 6501; Montell society makes)

Calcium stearate 0.05

Four [methylene radical-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] methane 0.1

Tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester 0.1

HALS:3,9-two [1, and 1-dimethyl-2-{ three (1,2,2,6,6-pentamethyl--4-

Piperidyl oxygen ketonic oxygen) butyl ketonic oxygen } ethyl]-2,4,8,10-Si Evil spiral shell table 16

[5,5] undecane

UV light absorber 0.3

Table 16

????No.	HALS (mass parts)	UV light absorber	The weather-proof time (hour)	Huang Du
						500 hours	1500 hours
				Embodiment 6-1	????0.3			Compound N o.12	??3500	??4.0	??7.2
Embodiment 6-2	????0.3	Compound N o.14	??3500			??3.9	??7.4
				Embodiment 6-3	????0.3			Compound N o.16	??3500	??4.0	??7.0
Embodiment 6-4	????0.3	Compound N o.42	??3700			??3.8	??6.9
				Comparative example 6-1	????0.3			Comparative compound 1	??2300	??5.5	??15.5
Comparative example 6-2	????0.3	Comparative compound 4	??3200			??4.3	??7.7
				Comparative example 6-3	????0.3			-	??1400	??11.0	??21.0

Embodiment 7

Mixed 5 minutes according to following prescription 7 with mixing machine, obtain resin combination, with 25 rev/mins it is extruded processing under 250 ℃, obtain pellet, this pellet is made thick 2 millimeters test film through injection molding again under 240 ℃.In the black floor temperature is under the condition of 18 minutes rainfall cycles in 83 ℃, 120 minutes, with daylight atmospheric corrosion resistance trier this test film is carried out atmospheric exposure test.Estimate according to the yellow degree after on-test to 500 hour, after 1500 hours that records by the Hunter colorimeter with until producing the disruptive time.The results are shown in table 17.

(prescription 7) (unit: mass parts)

High density polyethylene(HDPE) 100 mass parts

(HI-ZEX; Mitsui Chemicals society system) 0.05

Calcium stearate

Four [methylene radical-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester] methane 0.1

Thio-2 acid distearyl ester 0.05

HALS: sebacic acid two (2,2,6,6-tetramethyl--4-piperidyl) ester table 17

UV light absorber 0.3

Table 17

????No.	HALS (mass parts)	UV light absorber	The weather-proof time	Huang Du
						500 hours	1500 hours
				Embodiment 7-1	????0.3			Compound N o.12	???3900	????3.9	????5.8
Embodiment 7-2	????0.3	Compound N o.42	???4100			????3.6	????5.5
				Comparative example 7-1	????0.3			Comparative compound 1	???2900	????4.3	????10.4
Comparative example 7-2	????0.3	Comparative compound 4	???3400			????4.5	????10.8
				Comparative example 7-3	????0.3			-	???1800	????7.4	????14.1

Embodiment 8

Mixed 5 minutes according to following prescription 8 with mixing machine, obtain resin combination, with 50 rev/mins it is extruded processing under 300 ℃, obtain pellet, this pellet is made thick 2 millimeters test film through injection molding again under 305 ℃.In the black floor temperature is under the condition of 18 minutes rainfall cycles in 83 ℃, 120 minutes, this test film is carried out 1200 hours atmospheric exposure test with daylight atmospheric corrosion resistance trier.Poor (Δ Y) with the yellow degree before yellow degree behind the colorimeter determination test of Hunter and the test.The results are shown in table 18.

Comparative example 8

According to making the test film that do not mix UV light absorber with embodiment 8 identical steps and with the test film of comparative compound as UV light absorber, carry out the weathering resistance evaluation identical with embodiment 8, the results are shown in table 18.

(prescription 8) (unit: mass parts)

Polyethylene terephthalate 100 mass parts

(NOVAPET 6010G30; Mitsubishi Heavy Industries Ltd plastics society system)

UV light absorber 0.5

Table 18

????No.	UV light absorber	????ΔY
			Embodiment 8-1	Compound N o.3	????2.1
Embodiment 8-2	Compound N o.29	????2.0
			Embodiment 8-3	Compound N o.32	????1.8
Comparative example 8-1	????-	Albefaction
			Comparative example 8-2	Comparative compound 2	????3.6
Comparative example 8-3	Comparative compound 3	????3.8

Embodiment 9

Mixed 5 minutes according to following prescription 8 with mixing machine, obtain resin combination, with 50 rev/mins it is extruded processing under 300 ℃, obtain pellet, this pellet is made thick 2 millimeters test film through injection molding again under 305 ℃.Carry out the weathering resistance evaluation identical with embodiment 9.The results are shown in table 19.

Comparative example 9

According to make the test film that do not mix UV light absorber with embodiment 9 identical steps and with comparative compound as ultraviolet test film, carry out the weathering resistance evaluation identical with embodiment 9.The results are shown in table 19.

(prescription 9) (unit: mass parts)

Polyethylene terephthalate 100 mass parts

(NOVADURAN 5010R5; Mitsubishi Heavy Industries Ltd plastics society system)

Decabrominated dipheny base oxide 0.1

UV light absorber 0.5

Table 19

????No.	UV light absorber	????ΔY
			Embodiment 9-1	Compound N o.3	????2.5
Embodiment 9-2	Compound N o.29	????2.3
			Embodiment 9-3	Compound N o.32	????2.2
Comparative example 9-1	????-	Albefaction
			Comparative example 9-2	Comparative compound 2	????4.0
Comparative example 9-3	Comparative compound 3	????3.5

Embodiment 10

With mixing machine according to 100 mass parts resin Compositions, 0.3 mass parts HALS: four (1,2,2,6,6-pentamethyl--4-piperidyl)-1,2,3, the UV light absorber shown in the table 20 of 4-butane tetracarboxylic acid esters and 0.3 mass parts was mixed 5 minutes, obtain resin combination, it is extruded processing with 25 rev/mins, obtain pellet, this pellet is made thick 2 millimeters test film through injection molding again under 240 ℃.The processing temperature of pellet, test film is shown in table 20.In the black floor temperature is that 83 ℃, the condition of no rain descend, and with daylight atmospheric corrosion resistance trier this test film is carried out atmospheric exposure test.According to before on-test with 1200 hours after by the Hunter colorimeter record poor (the Δ Y) of yellow degree estimate.The results are shown in table 20.

Comparative example 10

According to making with comparative compound as the test film of UV light absorber with embodiment 10 identical steps, carry out the weathering resistance evaluation identical with embodiment 10, the results are shown in table 20.

Table 20

????No.	Synthetic resins	UV light absorber	The pellet processing temperature (℃)	The test film processing temperature (℃)	Huang Du poor (Δ Y)
						Embodiment 10-1	??ABS	Compound N o.1	????230	????230	2.0
Embodiment 10-2	??ABS	Compound N o.42	????230	????230	2.2
						Comparative example 10-1	??ABS	Comparative compound 1	????230	????230	3.2
Comparative example 10-2	??ABS	Comparative compound 2	????230	????230	3.1
						Embodiment 10-3	??PPO	Compound N o.3	????300	????300	1.9
Embodiment 10-4	??PPO	Compound N o.42	????300	????300	2.0
						Comparative example 10-3	??PPO	Comparative compound 1	????300	????300	2.9
Comparative example 10-4	??PPO	Comparative compound 2	????300	????300	2.8
						Embodiment 10-5	Nylon 6	Compound N 0.29	????250	????240	2.0
Embodiment 10-6	Nylon 6	Compound N 0.42	????250	????240	2.1
						Comparative example 10-5	Nylon	Comparative compound 1	????250	????240	3.0
Comparative example 10-6	Nylon	Comparative compound 3	????250	????240	2.8
						Embodiment 10-7	??PMMA	Compound N o.32	????220	????220	1.8
Embodiment 10-8	??PMMA	Compound N o.42	????220	????220	1.9
						Comparative example 10-7	??PMMA	Comparative compound 1	????220	????220	2.8
Comparative example 10-8	??PMMA	Comparative compound 3	????220	????220	2.9

ABS:STYRAK 100: industry society of Asahi Chemical Industry system

PPO:ZYLON 500H; Industry society of Asahi Chemical Industry system

Nylon 6:NOVAMID 1020A7; Mitsubishi Heavy Industries Ltd plastics society system

PMMA:DELPET 60N; Industry society of Asahi Chemical Industry system

The possibility of industrial application

According to the present invention, can make with resin Composition intermiscibility and/or favorable dispersibility, the ultra-violet absorber of the triazine based compound formation of abundant additive effect can be provided, thereby can make the improved products formed compound resin compositions such as weatherability, turbidity, bloom.

Claims

(according to the modification of the 19th of treaty)

1. synthetic resins UV light absorber, it comprises the represented triaizine compounds of following general formula (I)

In the general formula (I), R is that carbonatoms is 1～4 alkyl, and n is 0～2 integer, and X is the group that is selected from following (a)～(d),

(a)

(b)

(c)

(d)

In above-mentioned (a)～(d), R ¹Being that carbonatoms is 5～60 fatty group, is 5～8 o'clock at the carbonatoms of fatty group, R ¹For being selected from alicyclic radical and endways or have the group of the alkyl of alicyclic radical in the chain,

At carbonatoms is 9～19 o'clock, R ¹For being selected from the alkyl that has alicyclic radical in alicyclic radical, end or the chain and the group of 1-alkyl alkane-1-base,

At carbonatoms is 20～60 o'clock, R ¹For being selected from the alkyl that has alicyclic radical in alicyclic radical, end or the chain, having the alkyl of side chain and the group of straight chained alkyl;

R ²Be be selected from carbonatoms be 1～18 have side chain or endways or have the alkyl of alicyclic radical and the group of (many) alkoxyalkyls in the chain, described carbonatoms also comprises alicyclic radical;

R ' is that carbonatoms is 5～60 aliphatics two bases, is 5～8 o'clock at the carbonatoms of fatty group, and R ' is for being selected from alicyclic radical and endways or have the group of the alkane 2 basis of alicyclic radical in the chain,

At carbonatoms is 9～19 o'clock, and R ' is selected from the group that has the alkane 2 basis of alicyclic radical in alicyclic radical, end or the chain and have the alkane 2 basis of side chain,

At carbonatoms is 20～60 o'clock, and R ' is the group that is selected from the alkane 2 basis of the alkane 2 basis that has alicyclic radical in alicyclic radical, end or the chain, the alkane 2 basis with side chain and straight chain;

Wherein identical in R, n and the above general formula (I).

2. synthetic resins UV light absorber as claimed in claim 1 is characterized in that, the X in the described general formula (I) is the group of using (a) or (d) representing.

3. synthetic resins UV light absorber as claimed in claim 1 or 2 is characterized in that, at described general formula (I) with in general formula (I) in the represented group of X, n is 0.

4. compound resin composition is characterized in that, mixes any in 0.001～25 mass parts claim 1～3-described synthetic resins UV light absorber in 100 mass parts synthetic resins.

5. compound resin composition as claimed in claim 4 is characterized in that, at least a hindered amine that also mixes 0.001～10 mass parts is a photostabilizer.

6. as claim 4 or 5 described compound resin compositions, it is characterized in that described synthetic resins is selected from polycarbonate resin, polyolefin resin, polyester resin.

Revised the claim 1 in claims, with " at carbonatoms is, R at 9～19 o'clock ¹For being selected from the group that has the alkyl of alicyclic radical in alicyclic radical, end or the chain and have the alkyl of side chain " change that " at carbonatoms is, R at 9～19 o'clock ¹For be selected from alicyclic radical, endways or have the alkyl of alicyclic radical and the group of 1-alkyl alkane-1-base in the chain ".

Claims (6)

1. synthetic resins UV light absorber, it comprises the represented triaizine compounds of following general formula (I)

In the general formula (I), R is that carbonatoms is 1～4 alkyl, and n is 0～2 integer, and X is the group that is selected from following (a)～(d),

In above-mentioned (a)～(d), R ¹Being that carbonatoms is 5～60 fatty group, is 5～8 o'clock at the carbonatoms of fatty group, R ¹For being selected from alicyclic radical and endways or have the group of the alkyl of alicyclic radical in the chain,

At carbonatoms is 9～19 o'clock, R ¹For being selected from the group that has the alkyl of alicyclic radical in alicyclic radical, end or the chain and have the alkyl of side chain,

At carbonatoms is 20～60 o'clock, R ¹For being selected from the alkyl that has alicyclic radical in alicyclic radical, end or the chain, having the alkyl of side chain and the group of straight chained alkyl;

R ²Be be selected from carbonatoms be 1～18 have side chain or endways or have the alkyl of alicyclic radical and the group of (many) alkoxyalkyls in the chain, described carbonatoms also comprises alicyclic radical;

R ' is that carbonatoms is 5～60 aliphatics two bases, is 5～8 o'clock at the carbonatoms of fatty group, and R ' is for being selected from alicyclic radical and endways or have the group of the alkane 2 basis of alicyclic radical in the chain,

At carbonatoms is 9～19 o'clock, and R ' is selected from the group that has the alkane 2 basis of alicyclic radical in alicyclic radical, end or the chain and have the alkane 2 basis of side chain,

At carbonatoms is 20～60 o'clock, and R ' is the group that is selected from the alkane 2 basis of the alkane 2 basis that has alicyclic radical in alicyclic radical, end or the chain, the alkane 2 basis with side chain and straight chain;

Wherein identical in R, n and the above general formula (I).

2. synthetic resins UV light absorber as claimed in claim 1 is characterized in that, the X in the described general formula (I) is the group of using (a) or (d) representing.

3. synthetic resins UV light absorber as claimed in claim 1 or 2 is characterized in that, at described general formula (I) with in general formula (I) in the represented group of X, n is 0.

4. compound resin composition is characterized in that, mixes any one described synthetic resins UV light absorber in 0.001～25 mass parts claim 1～3 in 100 mass parts synthetic resins.

5. compound resin composition as claimed in claim 4 is characterized in that, at least a hindered amine that also mixes 0.001～10 mass parts is a photostabilizer.

6. as claim 4 or 5 described compound resin compositions, it is characterized in that described synthetic resins is selected from polycarbonate resin, polyolefin resin, polyester resin.