CN108350213A - Light diffusing articles - Google Patents
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- CN108350213A CN108350213A CN201680063780.1A CN201680063780A CN108350213A CN 108350213 A CN108350213 A CN 108350213A CN 201680063780 A CN201680063780 A CN 201680063780A CN 108350213 A CN108350213 A CN 108350213A
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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
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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
- C08L2205/24—Crystallisation aids
- C08L2205/242—Beta spherulite nucleating agents
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Abstract
The present invention relates to light diffusing articles, preferably piece, pipe or light bulb, and it includes polypropene composition, the polypropene composition includes acrylic polymer, and wherein polypropene composition is β nucleation.Include the shell of the light diffusing articles containing light source and the present invention the invention further relates to luminaire, the product is positioned relative to light source so that light source diffuses at least part of the light from the light source.
Description
The present invention relates to light diffusing articles and include the luminaires of the light diffusing articles.
By the way that organic or inorganic light diffusing agent is dispersed in transparent resin such as aromatic polycarbonate resin, acrylic resin
Or the material prepared in styrene resin has been widely used in needing the application field of light diffusion property.Application field includes adopting
Light shield, display, automobile instrument and panel.In these transparent resins, aromatic polycarbonate resin is widely used as having good
Resin, heat resistance and the against weather of good engineering properties, the resin of high transparency.For example, EP2829574 is disclosed comprising poly-
The light diffusion resin composition of carbonic ester.
Known to use the organic granular with cross-linked structure as light diffusing agent, example includes crosslinked acrylic acid
Grain, crosslinked polysiloxane series particle and crosslinked polystyrene particle.In addition, also using inorganic particle such as calcium carbonate, sulphur
Sour barium, aluminium hydroxide, silica, titanium dioxide and calcirm-fluoride and inorfil such as staple glass fibre.
It is also known that polypropylene is used to manufacture the purposes of light diffusing board.For example, WO2010074312 is disclosed comprising polypropylene
The light diffusing board of resin and hindered amine light stabilizer with specific chemical constitution.WO2010074312 is mentioned, light diffusing board
Include preferably further light diffusion particles and/or nucleating agent.Nucleating agent is that sorbierite system nucleating agent, organophosphorus ester are tied to form core
Agent, the nucleating agent of carboxylic metallic salt and rosin series nucleating agent.
JP5887024 discloses the polypropylene expanded film of the nucleating agent comprising glucitol derivative, has less than 6%
Light scattering index and mist degree less than 1%.JP5887024 uses polyacrylic α-nucleation to obtain low diffusion, without being to provide
Light diffusing patch.
Divide range degree to obtain high light, needs the diffusion agent of high load.However, this causes cost to increase, and reduce
Light transmittance.
It is an object of the present invention to solve above-mentioned and/or other problems.
Therefore, the present invention provides light diffusing articles, preferably piece, pipe or light bulb, described poly- it includes polypropene composition
Propylene compositions include acrylic polymer, and wherein polypropene composition is beta-nucleated.
It is beta-nucleated according to polypropene composition used in the present invention.It was surprisingly found that beta-nucleated poly- third
Ene compositions itself play a role as light diffusing agent.On the contrary, the polypropene composition of α-nucleation is sent out not as light diffusing agent
The effect of waving, therefore the light diffusing patch made of the polypropylene of α-nucleation needs other light diffusing agent.According to the present invention, due to making
For the presence for the beta-nucleated PP that light diffusing agent plays a role, the other light diffusing agent of use or use are less amount of in addition
Light diffusing agent, product can be obtained, have the function of high light diffusion.
It should be pointed out that US2010285251 discloses polypropene composition, it includes (a) Noblens and (b) nothing
Propene-1-butene copolymer or random propylene-ethylene copolymer are advised, ethylene contents are no more than 3.0wt.%, wherein polypropylene group
It is beta-nucleated to close object.According to US2010285251, polypropene composition by keeping rigidity and impact strength in high level,
The pipe with excellent pressure test performance can be produced.US2010285251 does not relate to light diffusion.
It is beta-nucleated
The polypropene composition of the present invention is beta-nucleated, that is, polypropene composition must be part in terms of β-modification
Crystallization.It is preferred that the amount of β-modification of polypropene composition is at least 10% measured by differential scanning calorimetry (DSC), more
Preferably at least 20%, still more preferably at least 30%, still more preferably at least 40%, still more preferably at least 50%, still more
Preferably at least 60%, still more preferably at least 70%.
The amount of β-modification is measured by differential scanning calorimetry (DSC).DSC is according to 3146/ third portions of ISO/method C2
(ISO 3146/part 3/method C2) is run, and sweep speed is 10 DEG C of ./min.By following formula by the second heat
(second heat) calculates the amount of β-modification：β areas/(α area+β areas).
In the temperature higher than 150 DEG C start to be changed into more stable alpha-modified, a thus part since thermodynamics β is modified
β modifications are shifted in dsc measurement heating process.Therefore, when being measured according to the method for the Turner-Jones of WAXS
(A.Turner-Jones et al., Makromol.Chem 75 (1964) 134), it is relatively low by the polyacrylic amounts of the β-of dsc measurement.
" second heat " refers to continue at the first time according to 3146/ third portions of ISO/method C2 heating samples, then with 10 DEG C/
The rate of min is cooled to room temperature.Then also according to 3146/ third portions of ISO/method C2, sample is heated for second.This second
Heat is related to measurement and calculating.
" first heat " in the process, all thermal histories for generating the sample of different crystalline texture are destroyed, the difference
Crystalline texture typically from different processing conditions and/or method.Use the second heat for measuring β-crystallinity, so that it may
With comparative sample, no matter the method for initially manufactured sample.
Polypropylene-based polymer
Homopolymer and homogeneous copolymers
Polypropylene-based polymer can be Noblen or the propylene including random copolymer He (more) block copolymer
Alpha olefin copolymer.Copolymer is preferably random copolymer.Total weight based on acrylic polymer, copolymer can be by least
The alpha-olefin of the propylene of 70wt% and at most 30wt% form.It is preferred that the alpha-olefin in propylene-alpha-olefin copolymers, which is selected from, has 2
Or the alpha-olefin of 4-10 carbon atom, such as ethylene, 1- butylene, 1- amylenes, 4-methyl-1-pentene, 1- hexenes, 1- heptene or 1-
Octene, optimal ethylene.
Therefore, for the purpose of the present invention, ethylene is considered as alpha-olefin.
The amount preferred 1-15wt%, more preferable 1-10wt%, more preferable 1- of alpha-olefin in propylene-alpha-olefin copolymers
6wt%, more preferable 1-4wt%.
Preferably, propylene-alpha-olefin copolymers are Propylene-ethylene random copolymers, wherein based on acrylic polymer
The amount of total weight, ethylene is 1-15wt%, more preferable 1-10wt%, more preferable 1-6wt%, more preferable 1-4wt%.
Preferably, Noblen or propylene alpha olefin copolymer are according to ISO1183-1:2012 density that measure are
0.8900-0.9100g/cm3, such as 0.8960-0.9040g/cm3。
Heterophasic propylene copolymers
Preferably, polypropylene-based polymer is heterophasic propylene copolymers.It was found that：The presence of both discrete phase and dispersed phase is led
Higher dispersion performance is caused.While not wanting to be bound by theory, the difference of the reflectivity between discrete phase and dispersed phase causes
Higher diffusive properties.
Heterophasic propylene copolymers, also referred to as anti-impact type propylene copolymer or propylene-based block copolymer are the important of polymer
Type, this is because attractive group of impact strength and its low cost of its engineering properties for example under wide scope stabilization
It closes.These copolymers have a wide range of applications：From consumer industrial (such as packaging and household utensil), auto industry to electrically answering
With.
Heterophasic propylene copolymers usually pass through the presence in catalyst in the concatenated reactor of two or more
Lower polypropylene (or propylene and alpha-olefin) and the then preparation of polymerizing ethylene-alpha olefin mixture.The polymer substance of generation is
Multiphase, but specific form generally depends on preparation method and monomer ratio used.
The heterophasic propylene copolymers used in the method for the present invention can use well known by persons skilled in the art any normal
It is prepared by rule technologies, for example, multi-stage method polymerization such as bulk polymerization, gas-phase polymerization, slurry polymerisation, polymerisation in solution or its
What is combined.Any conventional catalyst system can be used, for example, Ziegler-Natta or metallocene.It describes in the following
Such technology and catalyst：Such as WO06/010414, Polypropylene and other Polyolefins, by Ser
Van der Ven, Studies in Polymer Science 7, Elsevier 1990, WO06/010414, US4399054
And US4472524.Preferably, heterophasic propylene copolymers are prepared using Ziegler-Natta catalyst.
Heterophasic propylene copolymers can be prepared by the following method, the method includes：
Polypropylene and optional alpha-olefin in the presence of catalyst system, to obtain propylene matrix；With
Then in propylene matrix in the presence of catalyst system polymerising ethylene and alpha-olefin, with obtain dispersion
Ethene-alpha-olefin copolymer.These steps preferably carry out in different reactors.For first step catalyst system and
Catalyst system for second step can be similar and different.
Heterophasic propylene copolymers are made of the ethene-alpha-olefin copolymer of propylene matrix and dispersion.Propylene matrix is logical
The continuous phase in heterophasic propylene copolymers is commonly formed.Propylene matrix and the amount of the ethene-alpha-olefin copolymer of dispersion can be with
Pass through13C-NMR is measured, as known in the art.
Heterophasic propylene copolymers are made up of：
(a) propylene matrix,
Wherein propylene matrix is made of Noblen and/or propylene-alpha-olefin copolymers, the propylene-alpha-olefin
Copolymer is made of at least alpha-olefin of the propylene of 70wt% and at most 30wt% of the total weight based on propylene matrix, and
Wherein propylene matrix exists with the amount of the 60-95wt% based on total heterophasic propylene copolymers；With
(b) ethene-alpha-olefin copolymer disperseed,
The ethene-alpha-olefin copolymer wherein disperseed is deposited with the amount of the 40-5wt% based on total heterophasic propylene copolymers
, and
Wherein in heterophasic propylene copolymers the total amount of the ethene-alpha-olefin copolymer of the total amount and dispersion of propylene matrix it
With for 100wt%.
Propylene matrix is made of Noblen and/or propylene-alpha-olefin copolymers, the propylene-alpha-olefin copolymerization
Object is made of at least alpha-olefin of the propylene of the 70wt% and at most 30wt% such as ethylene of the total weight based on propylene matrix,
Such as be made of at least alpha-olefin of the propylene of 80wt% and at most 20wt%, such as by at least propylene of 90wt% and at most
The alpha-olefin of 10wt% forms.
It is preferred that the alpha-olefin in propylene-alpha-olefin copolymers is selected from the alpha-olefin with 2 or 4-10 carbon atom, such as second
Alkene, 1- butylene, 1- amylenes, 4-methyl-1-pentene, 1- hexenes, 1- heptene or 1- octenes, optimal ethylene.
It is preferred that propylene matrix is made of Noblen.
Based on total heterophasic propylene copolymers, the amount of propylene matrix is 60-95wt%, such as 65-85wt%, such as
70-85wt%, such as 70-80wt%, such as 65-75wt% or 75-85wt%.
Propylene matrix is preferably hemicrystalline, it means that it is not 100% unbodied, nor 100% crystallization.
For example, propylene matrix is at least 30%, and for example, at least 40% crystallization, for example, at least 50%, for example, at least 60% crystallization, and/
Or such as at most 80% crystallization, such as at most 70% crystallization.For example, the crystallinity of propylene matrix is 60-70%.For this hair
Bright purpose, according to 1997 ISO11357-1 and ISO11357-3, using differential scanning calorimetry (DSC), using 10 DEG C/
Scan rate, 5mg samples and the second heating curves of min is used as the theoretical standard of 100% crystalline material 207.1J/g, measures
Propylene matrix.
In addition to propylene matrix, heterophasic propylene copolymers further include the ethene-alpha-olefin copolymer of dispersion.The second of dispersion
Alkene-alpha olefin copolymer is also referred to as " dispersed phase " in this application.Dispersed phase is embedded in multiphase third in the form of discontinuous
In alkene copolymer.The granularity of dispersed phase is usually 0.05-5.0 microns, and more typically 0.05-2.0 microns, this can pass through transmission
Electron microscopy (TEM) measures.
The amount of the ethene-alpha-olefin copolymer of dispersion is 40-5wt%.It is preferably based on total heterophasic propylene copolymerization
Object, the amount of the ethene-alpha-olefin copolymer of dispersion are at least 10wt%, for example, at least 15wt% or at least 17wt%, and/
Or at most 35wt%, such as at most 30wt% or 25wt%.These ranges lead to higher light diffusion property.
In the heterophasic propylene copolymers of the composition of the present invention, the total amount of propylene matrix and ethylene-α-alkene of dispersion
The sum of total amount of hydrocarbon copolymer is 100wt%.
It is preferably based on ethene-alpha-olefin copolymer, the amount of the ethylene in ethene-alpha-olefin copolymer is 20-
65wt%, such as 40-60wt%；For example, it is based on ethene-alpha-olefin copolymer, the amount of the ethylene in ethene-alpha-olefin copolymer
It is at least 30wt% and/or at most 55wt%.The higher amount of ethylene in dispersed phase causes between discrete phase and dispersed phase
The difference of the reflectivity of bigger, and then lead to higher light diffusion property.
Alpha-olefin in ethene-alpha-olefin copolymer is preferably selected from alpha-olefin with 3-8 carbon atom and its arbitrary mixed
Object is closed, the alpha-olefin in optimal ethylene-alpha olefin copolymer is selected from the alpha-olefin with 3-4 carbon atom and its arbitrarily mixes
Object, more preferable alpha-olefin are propylene, and in this case, ethene-alpha-olefin copolymer is ethylene-propylene copolymer.It can use
Make ethylene comonomer to form the example packet of the suitably alpha-olefin with 3-8 carbon atom of ethene-alpha-olefin copolymer
Include but be not limited to propylene, 1- butylene, 1- amylenes, 4-methyl-1-pentene, 1- hexenes, 1- heptene and 1- octenes.
Preferably, the amount of the ethylene in heterophasic propylene copolymers is the 3-40wt% based on heterophasic propylene copolymers, for example,
At least 5wt%.It is highly preferred that the amount of the ethylene in heterophasic propylene copolymers is at least 6wt%, more preferably at least 8wt%.
Preferably, the melt flow rate (MFR) of propylene matrix (mixes it at it with the other components of composition of the present invention
Before；MFIPP) it is at most 70dg/min, preferably up to 50dg/min, preferably up to 30dg/min, most preferably up to 20dg/min
(ISO 1133,230℃,2.16kg).Preferably, the melt flow rate (MFR) of propylene matrix is at least 0.1dg/min, at least
0.5dg/min, at least 1dg/min, at least 5dg/min or at least 10dg/min (1133,230 DEG C of ISO, 2.16kg).
Preferably, the ethene-alpha-olefin copolymer of dispersion melt flow rate (MFR) (its with the present invention composition its
Before his component mixing；MFIEPR) it is at least 0.001dg/min, at least 0.01dg/min, at least 0.1dg/min, at least
0.3dg/min, at least 0.7dg/min, at least 1dg/min, and/or such as at most 20dg/min, at most 15dg/min, at most
10dg/min, at most 5dg/min or at most 3dg/min.Consider the MFI (MFI of propylene matrixPP), heterophasic propylene copolymers
In the amount (matrix content) and heterophasic propylene copolymers of MFI (MFI multiphases) and the propylene matrix in heterophasic propylene copolymers
The amount (rubber content (RC)) of dispersed phase calculates the MFI (MFI of the ethene-alpha-olefin copolymer of dispersion according to the following formulaEPR)：
Preferably, the melt flow rate (MFR) (MFI multiphases) of heterophasic propylene copolymers is at most 50dg/min, at most 40dg/
Min, at most 30dg/min, at most 20dg/min or at most 15dg/min (1133,230 DEG C of ISO, 2.16kg).Preferably, more
The melt flow rate (MFR) of phase propylene copolymer is at least 0.1dg/min, at least 0.5dg/min, at least 1dg/min, at least 5dg/
Min or at least 10dg/min (1133,230 DEG C of ISO, 2.16kg).
MFI (the MFI for the propylene matrix being mentioned abovePP) and dispersion ethene-alpha-olefin copolymer MFI (MFIEPR)
Value be understood to heterophasic propylene copolymers mixed with nucleating agent and optional component with obtain the present invention composition before
Value.The value of the MFI (MFI multiphases) of heterophasic propylene copolymers refers to the final MFI of heterophasic propylene copolymers.In order to illustrate this
Point：If heterophasic propylene copolymers are not subjected to visbreaking or transformation, MFI multiphases by with peroxide melting mixing
The initial MFI values of heterophasic propylene copolymers.If heterophasic propylene copolymers are subjected to through the visbreaking with peroxide melting mixing
Cracking or transformation, MFI multiphases are the value of the heterophasic propylene copolymers after such visbreaking or transformation.
It has realized that：It is beta-nucleated particularly to occur in propylene matrix (a) compared in dispersed phase (b).Therefore,
In addition propylene matrix (a) is preferably required to crystallize more compared to dispersed phase (b) β-.
Preferably, heterophasic propylene copolymers are according to ISO1183-1:2012 density measured are 0.8900-0.9100g/
cm3, such as 0.8960-0.9040g/cm3。
Acrylic polymer can also be the combination of any of above acrylic polymer, for example, Noblen and multiphase
Propylene copolymer is with 1:99-99:1 or 50:The mixture or Noblen and random propylene-ethylene of 50 weight ratio are copolymerized
Object is with 1:99-99:1 or 50:The mixture of 50 weight ratio.
Nucleating agent
The amount of nucleating agent in composition is preferably based on the 0.0001-2.0wt% of total composition, for example, at least
0.001wt%, at least 0.002wt%, or at least 0.005wt%, for example, at least 0.025wt%, for example, at least 0.05wt%,
And/or such as at most 2.0wt%, such as at most 1.5wt%, such as at most 1.0wt%, at most 0.5wt%, at most 0.1wt%.
Described in such as US2010285251 and US8637625, the document passes through the suitable example of nucleating agent
With reference to being incorporated herein.
The suitable type of nucleating agent includes：
Dicarboxylic acid derivatives type diamide compound comes from C5-C8Cycloalkyl monoamines class or C6-C12Aromatic monoamine class and
C5-C8Aliphatic series, C5-C8Cyclic aliphatic or C6-C12Aromatic dicarboxylic acid class, such as
Bis--C of-N, N'-5-C8Naphthenic base -2,6- aphthalimide compound, such as N, N'- dicyclohexyls -2,6- naphthalene two
Formamide and N, N'- bicyclooctyl -2,6- aphthalimides,
Bis--C of-N, N-5-C8Naphthenic base -4,4- biphenyl diformamide compound, such as N, N'- dicyclohexyl -4,4- biphenyl
Formamide and N, N'- bicyclopentyl -4,4- biphenyl diformamides,
Bis--C of-N, N'-5-C8Naphthenic base-paraphenylene terephthalamide's amine compounds, such as N, N'- dicyclohexyl terephthalamides
And N, N'- dicyclopentylterephthalamide,
Bis--C of-N, N'-5-C8Naphthenic base-Isosorbide-5-Nitrae-hexamethylene diformamide compound, such as N, N'- dicyclohexyl-Isosorbide-5-Nitrae-
Hexamethylene diformamide and N, N'- dicyclohexyl-Isosorbide-5-Nitrae-hexamethylene diformamides,
Diamine derivative type diamide compound comes from C5-C8Naphthenic base monocarboxylic acid class or C6-C12Aromatic monocarboxylate's class
And C5-C8Cyclic aliphatic or C6-C12Aromatic diamine class, such as
-N,N-C6-C12Arlydene-is bis--benzamide compounds, such as N, N'- is bis- to phenylene-- and benzamide and N,
N'-1,5- naphthalene-bis--benzamide,
-N,N'-C5-C8Naphthenic base-is bis--benzamide, such as N, N'-1,4- pentamethylene-bis--benzamide and N, N'-
Isosorbide-5-Nitrae-hexamethylene-is bis--benzamide,
The p- C of-N, N-6-C12Bis--the C of arlydene-5-C8Cycloalkyl carboxamides compound, such as N, N'-1,5- naphthalenes-bis--ring
Hexane formamide and N, N'-1,4- phenylenes-bis--cyclohexane carboxamide, and
-N,N'-C5-C8Naphthenic base-is bis--cyclohexane carboxamide compound, such as N, N'-1, and 4- pentamethylene-bis--hexamethylene
Formamide and N, N'-1,4- hexamethylenes-bis--cyclohexane carboxamide,
Amino acid derivativges type diamide compound comes from C5-C8Alkyl, C5-C8Naphthenic base-or C6-C12Aryl ammonia
Base acid, C5-C8Alkyl, C5-C8Naphthenic base-or C6-C12Aromatic monocarboxylate's chlorine and C5-C8Alkyl-, C5-C8Naphthenic base-or
C6-C12The amidation process of aromatic monoamine, such as
- N- phenyl -5- (N- benzamidos) pentanamides and N- cyclohexyl -4- (N- cyclohexyl-carbonylamino) benzoyl
Amine.
In addition suitable nucleating agent is：
Quinacridone type compounds, such as
Quinacridone, dimethylquinacridone and dimethoxy quinacridone,
Quinacridonequinone type compound, such as
Quinacridone quinone, 5,12- dihydros (2,3b) acridine -7,14- diketone and quino (2,3b) acridine -6,7,13,
The mixed crystal and dimethoxy quinacridone quinone of 14- (5H, 12H)-tetrone, and,
Quinacridone type compound, such as
Quinacridone, dimethoxy quinacridone and dibenzo quinacridone.
Suitable nucleating agent still further is：
The dicarboxylate of the metal of periodic table Section II a races, such as cis--calcium salt of Δ 4- tetrahydrophthalic acids, heptan two
Acid calcium salt and suberic acid calcium salt；The mixture of dicarboxylic acids and the metal salt of periodic table Section II a races.
Suitable nucleating agent still further is：
The salt of the metal of the IIa races of periodic table and the imino acid of following formula：
Wherein x=1-4；R-H,-COOH,C1-C12Alkyl, C5-C8Naphthenic base or C6-C12Aryl, and Y-C1-C12Alkane
Base, C5-C8Naphthenic base or C6-C12The divalent C of aryl substitution6-C12Aromatic moieties, such as
The calcium salt of phthalyl glycine, the calcium salt of hexahydro phthalyl glycine, N- phthalyl alanine
Calcium salt and/or N-4- methyl phthalyl glycine calcium salt.
The example of nucleating agent described in US2010285251 and US8637625 is incorporated by reference herein.
Preferably, nucleating agent includes the calcium salt of dicarboxylic acids, and most preferably cis--Δ 4- tetrahydrophthalic acids are (also referred to as
Cis- -4- cyclohexene -1,2- dicarboxylic acids) calcium salt.
Including the nucleating agent compositions of cis--Δ 4- tetrahydrophthalic acid calcium salts are from GCH Technology Co.,
Ltd. commercially available with NAB-82, by cis--Δ 4- tetrahydrophthalic acids and calcium stearate (molar ratio 1:2, i.e. NAB-
82 25.7wt% is cis--Δ 4- tetrahydrophthalic acids calcium salt) composition.
Nucleating agent can be above-mentioned arbitrary combination.
Light diffusing agent
In some embodiments, polypropene composition includes seldom light diffusing agent or does not include light diffusing agent.For example, poly-
Propylene compositions include being less than 0.05wt%, less than 0.01wt% or less than 0.001wt% or 0wt% relative to total composition
Light diffusing agent.
In some embodiments, polypropene composition further includes light diffusing agent.Preferably, when it is present, light diffusing agent
Amount be 0.05-10.0wt%, more preferable 0.1-5.0wt%, more preferable 0.1-2.0wt% relative to total composition, it is more excellent
Select 0.1-1.0wt%.The light diffusing agent of higher amount leads to higher light diffusion property but lower total light transmission.
The light diffusing agent that any known type can be used, can be organic granular or inorganic particle.Organic granular
Representative instance is the polymer for including the cross-linked particles obtained by the non-crosslinked monomer of polymerization and crosslinkable monomer.
Preferred polymeric composition granule, and particularly preferably use cross-linked particles.It is used as non-crosslinked list in cross-linked particles
The example of body includes non-crosslinked vinyl monomer, such as acrylic monomer, styrenic monomers and acrylic list
Body and olefinic monomers.Acrylic monomer includes methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, third
Olefin(e) acid 2- ethylhexyls, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, first
Base 2-EHA and phenyl methacrylate, it is all these all to can be used alone or in combination.Wherein, particularly preferred first
Base methyl acrylate.
Styrenic monomers include styrene, ring-alkylated styrenes class such as α-methylstyrene, methyl styrene (vinyl
Toluene) and ethyl styrene and halogenated styrenes class such as brominated styrene, wherein particularly preferred styrene.Acrylic list
Body includes acrylonitrile and methacrylonitrile.
Olefinic monomers include ethylene and norbornene compound.In addition, the example of other copolymerisable monomers includes methyl
Glycidyl acrylate, N- methylmaleimidos and maleic anhydride.Organic crosslinked particles can have such as N- ethyls penta
The unit of imidodicarbonic diamide.
Wait for that the example for the crosslinkable monomers being applied in combination with non-crosslinked vinyl monomer includes divinylbenzene, methyl
Allyl acrylate, triallyl cyanurate, isocyanic acid triallyl, two (methyl) acrylic acid glycol esters, two (methyl) third
Olefin(e) acid binaryglycol ester, (methyl) propylene acid propylene glycol ester, two (methyl) acrylic acid 1,6-HD esters, trimethylolpropane
(methyl) acrylate, four (methyl) acrylate, pentaerythritols, bisphenol-A two (methyl) acrylate, two (methyl) acrylic acid
Two ring pentyl esters, two (methyl) acrylic acid dicyclopentenyl base esters and N- methylols (methyl) acrylamide.
Preferably, light diffusing agent is crosslinked organic silicon granule.
Organic silicon granule includes the three-dimensional polymer chain of following formula,
RxSiO2-(x/2) (I)
Wherein, x is the positive number more than or equal to 1, and each R independently is aliphatic hydrocarbyl, aromatic hydrocarbyl or unsaturated group.
Preferably, x is the positive number more than or equal to 1, specifically for 1-1.9, more particularly 1-1.5, even more particularly
For 1-1.2；Each R independently is organic group, such as aliphatic hydrocarbyl, such as methyl, ethyl or butyl；Or aromatic hydrocarbyl, example
Such as phenyl, may include or unsaturated group, such as vinyl.
In an exemplary embodiment, R is with 1-8, specifically for the alkyl of 1-5 carbon atom, more particularly first
Base.Specifically mentioned silicon resin particle includes methyl silsesquioxane (methylsilsequioxane).
The average grain diameter of crosslinked organic silicon granule is preferably 0.01-50 μm, more preferable 1-30 μm, more preferably 1.8-10
μm.When average grain diameter is less than 0.01 μm or is more than 50 μm, light diffusivity may become unsatisfactory.Average grain diameter refer to by
50% value (D50) for the overall particle size distribution that laser diffraction/scattering method obtains.The quantity of size distribution can be single or more
It is a.I.e., it is possible to combine the different cross-linked silicone particles of two or more different types of average grain diameters.It is preferable, however, that
Crosslinked organic silicon granule has narrow size distribution.It is preferred that cross-linked silicone particles are distributed as wherein all particles at least
70wt% is comprised in 1.8-2.2 μm of average particle size range.The shape of light diffusing agent is preferably from the viewpoint of light diffusion property
It is thought of as almost spherical (globular), more preferably almost spheroidal (spherical).Spherical shape includes oval shape
Shape.
The bulk specific gravity of organic silicon granule can be 0.35-0.67 kg/liter.
The refractive index of light diffusing agent is preferably 1.30-1.80, more preferably 1.33-1.70, more preferably 1.35-
1.65.When it is comprised in resin combination, satisfactory light diffusion function is shown.
Preferably, it according to ISO 9277-2010, is measured by BET nitrogen absorption techniques, the specific surface of cross-linked silicone particles
Product is at least 10m2/ g, preferably at least 20m2/ g, preferably at least 30m2/g。
It includes Toshiba Silicone Co., Ltd. to be suitable for the invention commercially available silicon-type light diffusion particulate
TOSPEARL series, Dow Corning Toray Co. TORAYFIL series and Shin-Etsu Chemical Co.,
Ltd. organosilicon powder.
Other optional components
The composition of the present invention can optionally include at least one other component.The example of optional component is peroxidating
Object and other additives.The amount of optional component is usually the 0-30wt% of total composition.
It is appreciated that not influencing the degree for needing property of acquisition light-diffusing film or pipe to them using optional component.Example
Such as, being used as the additive of α-nucleating agent should not utilize according to the present invention.
Peroxide
In some embodiments, composition of the invention can be by by peroxide and acrylic polymer and nucleation
Agent melting mixing and obtain.The composition obtained by peroxide is added has to be gathered with the propylene for being used to prepare composition
Close different (higher) MFI of the MFI of object (especially heterophasic copolymer).The step is also referred to as visbreaking in the art
Cracking or transformation.Term " visbreaking " is well known in the field of the invention.For example, the method for visbroken polypropylene is
Through being disclosed in US 4,282,076 and EP 0063654.It is below and possible：Peroxide is polymerize with propylene first
Object melting mixing, the acrylic polymer change the melt flow index of heterophasic propylene copolymers, are then mixed with nucleating agent.
The example of organic peroxide is well known, and includes dialkyl peroxide class, such as diisopropylbenzene (DIPB) peroxidating
Object, peroxy ketal class, peroxycarbonic acid esters, diacyl peroxide, peroxide esters and peroxydicarbonates.Spy in these
It includes benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide to determine example
Object, 2,5- dimethyl -2,5- two (perbenzoic acid root (peroxybenzoato)) -3- hexenes, bis- (t-butyl peroxies of 1,4-
Change isopropyl) benzene, lauroyl peroxide, t-butyl peroxy-acetate, α, α '-two (t-butylperoxy) diisopropylbenzene (DIPB) (802), (the t-butylperoxy) -3- of 2,5- dimethyl -2,5- two hexenes, two (uncles of 2,5- dimethyl -2,5-
Butyl peroxy)-hexane, t-butyl perbenzoate, the peroxide phenylacetic acid tert-butyl ester, excessively secondary octanoic acid ter-butyl ester, cross neopentanoic acid uncle
Butyl ester crosses neopentanoic acid isopropyl phenyl ester.
Those skilled in the art can be easily by routine experiment it is determined that using how many peroxide to be had
There is the composition of required melt flow index.This also depends on the half-life period of peroxide and the condition for melting mixing,
And then depending on the exact composition of the heterophasic propylene copolymers.
When peroxide was used, the amount of peroxide is usually the 0.02-0.5wt%'s based on heterophasic propylene copolymers
Range.
In some embodiments, the composition of the present invention is prepared without using peroxide.
Additive
The composition of the present invention may further include additive.The additive may include as described in elsewhere
Light diffusing agent and nucleating agent.Additive may include stabilizer, such as heat stabilizer, antioxidant, UV stabilizer；Coloring
Agent, such as pigment and dyestuff；Fining agent；Surface tension modifier；Lubricant；Fire retardant；Releasing agent；Flow improving agent；Plasticizer；
Antistatic agent；Exterior elastomer impact modifying agent；Foaming agent；Inorganic filler and reinforcing agent；And/or enhancing polymer and filler it
Between interface cohesion component, such as the polypropylene of maleation.
Those skilled in the art can be readily selected the appropriate combination of any additive and the amount of additive, without
Excessively experiment.The amount of additive depends on their type and function, typically from 0- about 30wt%.The amount of additive is based on
Total composition can be about 1- about 20wt%, about 2- about 10wt% or about 3- about 5wt%.
In the method for the invention in order to formed all components being added comprising the composition of acrylic polymer, nucleation
The summation of agent and optional components should add up as 100wt%.
Preferably, the total amount of acrylic polymer and nucleating agent is at least 70wt%, at least 80wt% of total composition, until
Few 90wt%, at least 95wt%, at least 97wt%, at least 98wt%, at least 99wt%, at least 99.5wt%, at least
99.9wt% or at least 100wt%.
Preferably, composition of the invention includes acid scavenger.Acid scavenger can be individually added into nucleating agent
Into the composition of the present invention.Additionally or alternatively, acid scavenger can be as comprising nucleating agent and acid scavenger
Composition is added into composition.Preferably, the amount of the acid scavenger in composition is the 0.01- relative to total composition
1wt%.Any of acid scavenger is suitable, and can be for example selected from Hydrotalcite (hydrotalcite), stearic acid
Calcium, odium stearate, zinc stearate, magnesium stearate and combinations thereof.
The invention further relates to the compositions for not including or including minimal amount of inorganic filler.Nothing in the composition of the present invention
The amount of machine filler can be at most 5wt%, at most 3wt%, at most 1wt%, at most 0.5wt%, at most 0.1wt% or 0wt%.
The invention further relates to do not include or comprising the minimal amount of additional set as acrylic polymer and nucleating agent
The composition of the polypropylene homopolymer divided.The amount of polypropylene homopolymer in the composition of the present invention can be at most 5wt%, extremely
More 3wt%, at most 1wt%, at most 0.5wt%, at most 0.1wt% or 0wt%.
In some embodiments, composition of the invention includes that inorganic filler or glass fibre are used as and propylene gathered
Close the additional component of object and nucleating agent.The amount of inorganic filler or glass fibre can be such as 5-30wt%, such as 10-
25wt%, such as 15-20wt%.The invention further relates to do not include or comprising it is minimal amount of as acrylic polymer and at
The inorganic filler of the additional component of core agent or the composition of glass fibre.The amount of inorganic filler or glass fibre can be at most
5wt%, at most 3wt%, at most 1wt%, at most 0.5wt%, at most 0.1wt% or 0wt%.
In some embodiments, composition of the invention includes as the additional of acrylic polymer and nucleating agent
Component impact modifying agent such as ethene-alpha-olefin copolymer.The amount of impact modifying agent can be such as 5-30wt%, such as
10-25wt%, such as 15-20wt%.The invention further relates to do not include or comprising minimal amount of as acrylic polymer
With the composition of the impact modifying agent such as ethene-alpha-olefin copolymer of the additional component of nucleating agent.The composition of the present invention
The amount of middle impact modifying agent such as ethene-alpha-olefin copolymer can be at most 5wt%, at most 3wt%, at most 1wt%, at most
0.5wt%, at most 0.1wt% or 0wt%.
Light diffusing articles
The light diffusing articles of the present invention are not porous articles.Therefore, the light diffusing articles phase is being formed by polypropene composition
Between density it is substantially constant.On the contrary, for example polymer composition it is biaxial stretch-formed made of perforated membrane have than polymerization
The much lower density of compositions.
Preferably, light diffusing articles of the invention are injection-molded item.Injection molding will not lead to porous article.
Preferably, light diffusing articles of the invention have density da, acrylic polymer is with density dp, | dp-da|/dpFor
At most 1%, such as at most 0.5%, wherein according to ISO1183-1:2012 measure daAnd dp。
Preferably, light diffusing articles of the invention are according to ISO1183-1:2012 density measured are 0.8900-
0.9100g/cm3, such as 0.8960-0.9040g/cm3。
Preferably, the polypropene composition of light diffusing articles of the invention is according to ISO1183-1：2012 density that measure are
0.8900-0.9100g/cm3, such as 0.8960-0.9040g/cm3。
Preferably, the acrylic polymer of the polypropene composition of light diffusing articles of the invention is according to ISO1183-1:
2012 density measured are 0.8900-0.9100g/cm3, such as 0.8960-0.9040g/cm3。
The light diffusing articles of the present invention have thickness small for light as commonly understood in the art is from lit transmissive.This
The light diffusing articles of invention can have any shape, but common example includes light diffusing patch, light diffusion pipe and light diffusion lamp
Bubble.
In general, the thickness of product is 0.2-10mm, such as 0.2-5mm, 0.5-5mm or 0.8-3mm.
Term " piece " is understood to mean in this application with small thickness and in two dimensions perpendicular to thickness direction
The product extended on degree.When the thickness of " piece " is small, be, for example, less than 0.25mm when, should " piece " be also referred to as film.
Term " pipe " is understood as referring to the shape with hollow cylinder, in axis direction in this application
The product of small thickness.
Term " light bulb " is general in the art it is understood that the i.e. shell of light source such as LED light.
The present invention also provides the methods for the light diffusing articles for preparing the present invention, including by acrylic polymer and beta-nucleated
Agent melting mixing is to obtain composition and composition is formed light diffusing articles.
Property
Preferably, the melt flow rate (MFR) of the polypropene composition in light diffusing articles of the invention is at most 50dg/
Min, at most 40dg/min, at most 30dg/min, at most 20dg/min or at most 15dg/min (1133,230 DEG C of ISO,
2.16kg).Preferably, the melt flow rate (MFR) of composition of the invention is at least 0.1dg/min, at least 0.5dg/min, at least
1dg/min, at least 5dg/min or at least 10dg/min (1133,230 DEG C of ISO, 2.16kg).Preferably, combination of the invention
The melt flow rate (MFR) of object is 5-50dg/min (1133,230 DEG C of ISO, 2.16kg).
In the context of the present invention, light diffusion property is indicated by light dispersion degree (DLD), and wherein DLD is defined as obtaining
Equal to the acceptance angle of the luminous intensity of the half of normal transmission light luminous intensity.Luminous intensity can be by goniophotometer for example
The GP200 of transmission-type is measured.
In the context of the present invention, optical transparency and mist degree are measured according to ASTM D1003.
Preferably, the light dispersion degree (DLD) of the polypropene composition in light diffusing articles of the invention is：It is as thickness
The piece of 1mm is measured as at least 10 degree, at least 15 degree, at least 20 degree, at least 25 degree, at least 30 degree, at least 35 degree, at least 40 degree,
At least 44 degree, at least 45 degree, at least 47.5 degree or at least 50 degree；And/or the DLD measured as the piece that thickness is 1.5mm is extremely
It is 10 degree few, at least 15 degree, at least 20 degree, at least 30 degree, at least 40 degree, at least 50 degree, at least 56 degree or at least 57 degree.
Preferably, the light transmittance of the polypropene composition in light diffusing articles of the invention is：As the piece that thickness is 1mm
It is measured as at least 55% or at least 65%；The light transmittance that measures of piece for being 1.5mm as thickness is at least 45% or at least 55%.
Preferably, the mist degree of the polypropene composition in light diffusing articles of the invention is：It is surveyed as the piece that thickness is 1mm
Be at least 75%, at least 90% or at least 98%, and/or the mist degree that measures of the piece for being 1.5mm for thickness be at least 85%,
At least 90% or at least 98%.
Heterophasic propylene copolymers
Preferably, (wherein acrylic polymer is described herein to the polypropene composition in light diffusing articles of the invention
Heterophasic propylene copolymers) light dispersion degree (DLD) be：At least 44 degree, at least 45 degree are measured as the piece that thickness is 1mm,
At least 47.5 degree or at least 50 degree；And/or it is at least 56 degree or at least 57 degree to measure DLD as the piece that thickness is 1.5mm.So
And such composition can also have lower light disperse minimum degree, such as above-mentioned at least 10 listed, 15,20,25,30,
35 or 40 degree.
Preferably, (wherein acrylic polymer is described herein to the polypropene composition in light diffusing articles of the invention
Heterophasic propylene copolymers) light transmittance be：It is measured as at least 65% as the piece that thickness is 1mm, and/or is as thickness
The light transmittance that the piece of 1.5mm measures is at least 55%.
Preferably, (wherein acrylic polymer is described herein to the polypropene composition in light diffusing articles of the invention
Heterophasic propylene copolymers) mist degree be：It is measured as at least 98% as the piece that thickness is 1mm, and/or is as thickness
The mist degree that the piece of 1.5mm measures is at least 98%.
In particularly preferred embodiments, polypropene composition (the wherein propylene in light diffusing articles of the invention
Polymer is heterophasic propylene copolymers as described herein) as the light dispersion degree (DLD) of the piece that thickness is 1mm it is at least 44
Degree, the light transmittance of piece for being 1mm as thickness is at least 65%, and the mist degree of piece for being 1mm as thickness is at least 98%.
Propylene-alpha-olefin copolymers
Preferably, (wherein acrylic polymer is described herein to the polypropene composition in light diffusing articles of the invention
Propylene-alpha-olefin copolymers) light dispersion degree (DLD) be：It is measured as at least 10 degree or at least 15 as the piece that thickness is 1mm
Degree, and/or as the DLD that the piece that thickness is 1.5mm measures be at least 10 degree or at least 15 degree.
Preferably, (wherein acrylic polymer is described herein to the polypropene composition in light diffusing articles of the invention
Propylene-alpha-olefin copolymers) light transmittance be：It is measured as at least 65% as the piece that thickness is 1mm, and/or as thickness
It is at least 55% for the light transmittance that the piece of 1.5mm measures.
Preferably, (wherein acrylic polymer is described herein to the polypropene composition in light diffusing articles of the invention
Propylene-alpha-olefin copolymers) mist degree be：It is measured as at least 75% or at least 90% as the piece that thickness is 1mm, and/or
The mist degree that measures of piece for being 1.5mm as thickness is at least 85%, at least 90% or at least 98%.
In particularly preferred embodiments, polypropene composition (the wherein propylene in light diffusing articles of the invention
Polymer is propylene-alpha-olefin copolymers as described herein) as the light dispersion degree (DLD) of the piece that thickness is 1.5mm it is at least
15 degree, the light transmittance of piece for being 1mm as thickness is at least 65%, and the mist degree of piece for being 1mm as thickness is at least 85%.
The invention further relates to the polypropene composition comprising acrylic polymer, (wherein polypropene composition is beta-nucleated
) it is used to prepare the purposes of light diffusing articles, preferably piece, pipe or light bulb.
The invention further relates to the purposes that piece, pipe or the light bulb of the present invention are used for diffused light.
The invention further relates to luminaires comprising the shell of the light diffusing articles containing light source and the present invention, the system
Condition positions light source so that it diffuses at least part of the light from the light source.Preferably, light source is LED light.
For purposes of illustration, although the present invention has been described in detail, it will be appreciated that such detailed description is only
For the purpose, those skilled in the art can be in the case where not departing from the spirit and scope invented defined in claim
Variation is made wherein.
It is further noted that the present invention relates to all possible combinations of feature described herein, particularly preferably weigh
The combination of those of feature present in profit requirement.Accordingly, it is to be understood that：This application describes the features for being related to the present composition
All combinations, be related to the method for the present invention all combinations of feature and the feature of the present composition and be related to present invention side
All combinations of the feature of method.
It should also be noted that term " include " or " contain " is not excluded for the presence of other elements.However, it should also be appreciated that
, the product/composition being grouped as by these groups is also disclosed that for the description of the product/composition comprising certain components.
It may be advantageous for the product/composition being grouped as by these groups, because it, which is provided, prepares the simpler of the product/composition
Single, more economical method.Similarly, it is understood that, the description of the method including certain steps is also disclosed that by these
The method of step composition.It may be advantageous for the method being made of these steps, because it provides simpler, more economical side
Method.
The present invention is illustrated by way of following embodiment now, however without being limited thereto.
Material
Acrylic polymer：
Polymer 1 is that the heterophasic propylene of the dispersed phase of the discrete phase comprising Noblen and propylene-ethylene copolymers is total
Polymers.
Polymer 2 is propylene-ethylene copolymers.
| Polymer 1 | Polymer 2 | |
| RC：The amount (w%) of dispersed phase | 19.1 | - |
| RCC2：The amount (w%) of ethylene in dispersed phase | 47.2 | - |
| The amount (w%) of ethylene in copolymer | 9 | 3.36 |
| MFR(g/10min) | 30 | 9 |
| Density (g/cm3) | 0.9016 | 0.9015 |
MFR is measured according to 1133,230 DEG C of ISO, 2.16kg.
According to ISO1183-1:2012 measure density.
Additive：
Sodium benzoate
α-nucleating agent compositions 1：Two (4- (tertiary butyl) benzoate anions-O) hydroxy Als, GCH TECHNOLOGY CO.,
LTD.；
α-nucleating agent compositions 2：Zinc stearate 34wt%, Ca HHPA 66wt%, Milliken；
Nucleating agent composition：Molar ratio is about 2:1 stearic calcium salt and cis--Δ 4- tetrahydrophthalic acids
The calcium salt calcium salt of cis--Δ 4- tetrahydrophthalic acids (25.7wt% be), GCH TECHNOLOGY CO., LTD.
In addition, having used antistatic agent, antioxidant 1 and antioxidant 2 as pointed by following table.
Acrylic polymer is blended in advance with additive.The powder being blended in advance is then squeezed out using double screw extruder.It will
Granule is 3 hours dry at 100 DEG C, is molded using FANUC injection molding machines (S-2000i) to prepare the component for test.
Equipment and program
Measurement for optical property, through the Hazegard II with standard D65 lamps according to ASTM D1003 schemes (not
Compensation model) obtain transmisivity data.Pass through goniophotometer GP-200 (the Goniophotometer GP- of transmission mode
200) light dispersion degree (DLD) is measured.Based on Lambert law, maximum DLD is 60 degree.
The amount of β-modification is measured by differential scanning calorimetry (DSC).DSC is according to 3146/ third portions of ISO/method C2
Operation, sweep speed are 10 DEG C of ./min.The amount of β-modification is calculated by the second heat by following formula：
β areas/(α area+β areas).
According to ISO 1183-1:2012 test densitys.
Composition and test result are shown in table 1-4.
Table 1：Polymer 1 with sodium benzoate
| Item description | Unit | #1 | #2 | #3 | #4 |
| Polymer 1 | Wt% | 99.6 | 99.525 | 99.51 | 99.5 |
| Sodium benzoate | Wt% | 0.075 | 0.09 | 0.1 | |
| Antistatic agent | Wt% | 0.25 | 0.25 | 0.25 | 0.25 |
| Antioxidant 1 | Wt% | 0.1 | 0.1 | 0.1 | 0.1 |
| Antioxidant 2 | Wt% | 0.05 | 0.05 | 0.05 | 0.05 |
| T%@1mm | % | 68.3 | 68.1 | 68.1 | 67.5 |
| Mist degree %@1mm | % | 98.1 | 98.1 | 98.2 | 98 |
| T%@1.5mm | % | 59.3 | 59.2 | 59.2 | 59.1 |
| Mist degree %@1.5mm | % | 98.1 | 98.2 | 98.2 | 98.1 |
| DLD@1mm | Degree | 43.6 | 35.9 | 32.3 | 40.4 |
| DLD@1.5mm | Degree | 55.6 | 55.6 | 55 | 55.7 |
| The amount of β-modification | % | 0 | 0 | 0 | 0 |
| The density of piece | g/cm3 | 0.9016 | 0.9019 | 0.9024 | 0.9025 |
Sodium benzoate is used as α-nucleating agent, and the effect for diffusing performance is shown in Table 1.It can be seen that：Pass through addition
Sodium benzoate, DLD are not improved.
Table 2：Polymer 1 with α-nucleating composition
| Item description | Unit | #5 | #6 | #7 | #8 | #9 | #10 | #11 |
| Polymer 1 | Wt% | 99.58 | 99.54 | 99.52 | 99.5 | 99.59 | 99.58 | 99.5 |
| α-nucleating agent compositions 1 | Wt% | 0.02 | 0.06 | 0.08 | 0.1 | |||
| α-nucleating agent compositions 2 | Wt% | 0.01 | 0.02 | 0.1 | ||||
| Antistatic agent | Wt% | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
| Antioxidant 1 | Wt% | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Antioxidant 2 | Wt% | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| T%@1mm | % | 69.1 | 68.5 | 68.9 | 68.5 | 68.4 | 68.4 | 68.8 |
| Mist degree %@1mm | % | 98.1 | 98.1 | 98.1 | 98 | 98 | 98.2 | 98.1 |
| T%@1.5mm | % | 59.5 | 59.8 | 60.2 | 59.6 | 59.1 | 59.5 | 59.8 |
| Mist degree %@1.5mm | % | 98.2 | 98.1 | 98.1 | 98.1 | 98.1 | 98.1 | 98.1 |
| DLD@1mm | Degree | 37.4 | 37.3 | 42.3 | 39.4 | 37.3 | 27.4 | 36.8 |
| DLD@1.5mm | Degree | 54.1 | 54.1 | 55.6 | 55.2 | 54.7 | 54.3 | 54.8 |
| The amount of β-modification | % | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| The density of piece | g/cm3 | 0.9012 | 0.9026 | 0.9015 | 0.902 | 0.9019 | 0.902 | 0.9023 |
In the experiment of table 2, other two kinds of α-nucleating agents are used.In both cases, it can be seen that：By adding
Enter α-nucleating agent, DLD is not improved.
Table 3：Polymer 1 with beta-nucleated composition
| Item description | Unit | #12 | #13 | #14 | #15 | #16 |
| Polymer 1 | Wt% | 99.58 | 99.56 | 99.54 | 99.52 | 99.5 |
| Nucleating agent composition | Wt% | 0.02 | 0.04 | 0.06 | 0.08 | 0.1 |
| Nucleating agent | Wt% | 0.00516 | 0.01032 | 0.01548 | 0.02064 | 0.0258 |
| Antistatic agent | Wt% | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 |
| Antioxidant 1 | Wt% | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Antioxidant 2 | Wt% | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| T%@1mm | % | 66.8 | 66.1 | 66.2 | 66.3 | 66.3 |
| Mist degree %@1mm | % | 98.1 | 98.1 | 98.1 | 98.1 | 98 |
| T%@1.5mm | % | 58.2 | 57.7 | 57.9 | 58.6 | 58.7 |
| Mist degree %@1.5mm | % | 98.1 | 98.2 | 98.1 | 98.1 | 98.1 |
| DLD@1mm | Degree | 46.3 | 49.9 | 49.5 | 52.6 | 51.4 |
| DLD@1.5mm | Degree | 57 | 57.6 | 57.7 | 57.4 | 57.5 |
| The amount of β-modification | % | 20.6 | 62.36 | 63.38 | 70.30 | 77.62 |
| The density of piece | g/cm3 | 0.8996 | 0.8976 | 0.8972 | 0.8975 | 0.8965 |
As can be seen from Table 3：Nucleating agent, which is added, leads to the increase of DLD.Especially with the thin slice of 1mm, the increase of DLD
It is especially big.The level of DLD increase to using light diffusing agent makrolon (referring to table 5) comparable level.Light transmittance maintains
In constant level.
Table 4：Polymer 2 with various nucleating agents
| Item description | Unit | #17 | #18 | #19 | #20 |
| Polymer 2 | Wt% | 99.65 | 99.6 | 99.6 | 99.6 |
| Sodium benzoate | Wt% | 0.05 | |||
| α-nucleating agent compositions 2 | Wt% | 0.05 | |||
| Nucleating agent composition | Wt% | 0.05 | |||
| Nucleating agent | Wt% | 0.0129 | |||
| Antistatic agent | Wt% | 0.25 | 0.25 | 0.25 | 0.25 |
| Antioxidant 1 | Wt% | 0.05 | 0.05 | 0.05 | 0.05 |
| Antioxidant 2 | Wt% | 0.05 | 0.05 | 0.05 | 0.05 |
| T%1mm | % | 89.4 | 89.1 | 88.6 | 82.5 |
| Mist degree %1mm | % | 49.2 | 22 | 28.4 | 91.6 |
| DLD@1mm | ° | 1.3 | 1.3 | 1.3 | 1.2 |
| DLD@1.5mm | ° | 1.4 | 1.3 | 1.3 | 16.5 |
| MFR | g/10min | 9.17 | 9.33 | 9.33 | 9.21 |
| Xia Shi impacts | kJ/m2 | 4 | 5.44 | 5.41 | 8.47 |
| Flexural modulus | MPa | 1088 | 1226 | 1212 | 884 |
| The amount of β-modification | % | 0 | 0 | 0 | 74.14 |
| The density of piece | g/cm3 | 0.9015 | 0.9022 | 0.9017 | 0.8981 |
Instead of the heterophasic propylene copolymers in table 1-3, acrylic polymer is that the ethylene-propylene in the experiment of table 4 is random
Copolymer.As in the experiment using heterophasic propylene copolymers, the increase of the use of α-nucleating agent without result in DLD.It compares
Under, under 1.5mm thickness the formation of β-form lead to the increase of DLD.The formation of β-form also results in the increase of impact strength
With the reduction of flexural modulus.
MFR is measured according to ISO1133 (2.16kg, 230 DEG C).
Xia Shi impact strengths are measured at 23 DEG C according to ISO 179.
Flexural modulus is measured at 23 DEG C according to ISO 178.
In addition, the optical property of the light diffusing patch of makrolon is as shown in table 5.
Table 5
| Item description | Unit | #21 | #22 |
| Makrolon, MFR 9g/10min | Wt% | 100 | 99 |
| Diffusion agent, organic silica bead | Wt% | 1 | |
| T%@1mm | % | 90.8 | 64.8 |
| Mist degree %@1mm | % | 1.9 | 98.4 |
| DLD@1mm | ° | 1.3 | 51.6 |
Claims (17)
1. light diffusing articles, preferably piece, pipe or light bulb, it includes polypropene composition, the polypropene composition includes propylene
Based polymer, wherein polypropene composition are beta-nucleated.
2. light diffusing articles according to claim 1, wherein the light diffusing articles are injection-molded item.
3. according to any one of them light diffusing articles of preceding claims, wherein the light diffusing articles have density da, institute
Stating acrylic polymer has density dp, | dp-da|/dpAt most 1%, wherein according to ISO1183-1:2012 measure daAnd dp。
4. according to any one of them light diffusing articles of preceding claims, wherein the institute measured by differential scanning calorimetry
The amount for stating β-modification of polypropene composition is at least 10%.
5. according to any one of them light diffusing articles of preceding claims, wherein the polypropene composition includes beta-nucleated
Agent, wherein it is preferred that the amount of nucleating agent relative to total composition be 0.0001-2.0wt%, preferably 0.001-2.0wt%, such as
At least 0.002wt%, at least 0.005wt%, at least 0.025wt% or at least 0.05wt%, and/or such as at most 1.5wt%,
Such as at most 1.0wt%, at most 0.5wt% or at most 0.1wt%.
6. according to any one of them light diffusing articles of preceding claims, wherein the polypropene composition is also unrestrained comprising light
Penetrate agent, wherein it is preferred that the amount of light diffusing agent relative to total composition be 0.05-10.0wt%.
7. according to any one of them light diffusing articles of preceding claims, wherein the polypropene composition includes seldom light
Diffusion agent does not include light diffusing agent, wherein it is preferred that the polypropene composition includes to be less than 0.05wt% relative to total composition
Light diffusing agent.
8. according to any one of them light diffusing articles of preceding claims, the thickness with 0.2-10mm.
9. according to any one of them light diffusing articles of claim 1-8, wherein the acrylic polymer is heterophasic propylene
Copolymer is made up of：
(a) propylene matrix, wherein the propylene matrix is made of Noblen and/or propylene-alpha-olefin copolymers, institute
State at least propylene of 70wt% and at most 30wt% of the propylene-alpha-olefin copolymers by the total weight based on the propylene matrix
Alpha-olefin composition, and
The wherein described propylene matrix exists with the amount of the 60-95wt% based on total heterophasic propylene copolymers；
(b) ethene-alpha-olefin copolymer disperseed, wherein the ethene-alpha-olefin copolymer of the dispersion is with based on total multiphase
The amount of the 40-5wt% of propylene copolymer exists, and
In the wherein described heterophasic propylene copolymers total amount of the ethene-alpha-olefin copolymer of the total amount and dispersion of propylene matrix it
With for 100wt%,
The acrylic polymer is according to ISO1183-1 preferably wherein:2012 density measured are 0.8900-0.9100g/cm3,
Such as 0.8960-0.9040g/cm3, and/or the wherein described polypropene composition is according to ISO1183-1:2012 density measured
For 0.8900-0.9100g/cm3, such as 0.8960-0.9040g/cm3。
10. light diffusing articles according to claim 9, wherein the amount of ethylene is base in the ethene-alpha-olefin copolymer
In the 20-65wt% of the ethene-alpha-olefin copolymer.
11. light diffusing articles according to claim 9 or 10, wherein the light dispersion degree (DLD) of the polypropene composition
For：It is measured as at least 44 degree, at least 45 degree as the piece that thickness is 1mm, at least 47.5 degree or at least 50 degree, and/or as thickness
The DLD that the piece that degree is 1.5mm measures is at least 56 degree or at least 57 degree, and wherein DLD is defined as obtaining the light equal to normal transmission
Value half value acceptance angle.
12. according to any one of them light diffusing articles of claim 9-11, wherein the light transmittance of the polypropene composition
For：It is measured as at least 55% as the piece that thickness is 1mm, and/or as the light transmittance that the piece that thickness is 1.5mm measures is at least
45%, wherein the light transmittance is measured according to ASTM D1003.
13. according to any one of them light diffusing articles of claim 9-12, wherein the mist degree of the polypropene composition is：
It is measured as at least 75% as the piece that thickness is 1mm, and/or as the mist degree that the piece that thickness is 1.5mm measures is at least 85%,
The wherein described mist degree is measured according to ASTM D1003.
14. according to any one of them light diffusing articles of claim 1-8, wherein the acrylic polymer is propylene-α-
Olefin copolymer, and the light dispersion degree (DLD) that the wherein described polypropene composition is measured as the piece that thickness is 1.5mm is at least
15 degree, the light transmittance that measures of piece for being 1mm as thickness is at least 55%, and the mist degree that measures of piece for being 1mm as thickness is extremely
Few 75%, the acrylic polymer is according to ISO1183-1 preferably wherein:2012 density measured are 0.8900-0.9100g/
cm3, such as 0.8960-0.9040g/cm3, and/or the wherein described polypropene composition is according to ISO1183-1:2012 measure it is close
Degree is 0.8900-0.9100g/cm3, such as 0.8960-0.9040g/cm3。
15. the polypropene composition comprising acrylic polymer is used to manufacture light diffusing articles, the preferably use of piece, pipe or light bulb
On the way, wherein the polypropene composition is beta-nucleated.
16. luminaire includes the shell of any one of them light diffusing articles containing light source and according to claim 1-14,
The product is positioned relative to light source so that it diffuses at least part of the light from the light source.
17. luminaire according to claim 16, wherein the light source is LED light.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15192513.8 | 2015-11-02 | ||
| EP15192513 | 2015-11-02 | ||
| PCT/EP2016/076100 WO2017076772A1 (en) | 2015-11-02 | 2016-10-28 | Light diffusing article |
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|---|---|---|---|
| CN201680063780.1A Pending CN108350213A (en) | 2015-11-02 | 2016-10-28 | Light diffusing articles |
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| WO (1) | WO2017076772A1 (en) |
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|---|---|---|---|---|
| CN111019238A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Polypropylene composition for lamps and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109438832A (en) * | 2018-10-08 | 2019-03-08 | 江苏恒隆通新材料科技有限公司 | A kind of light diffusing sheet and preparation method thereof and preparation method thereof |
| WO2023066851A1 (en) * | 2021-10-21 | 2023-04-27 | Borealis Ag | SYNERGISTIC ß-NUCLEATING BLENDS OF DICARBOXYLIC ACIDS WITH CALCIUM SALTS OF FULLY SATURATED FATTY ACIDS |
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| US20060177632A1 (en) * | 2005-02-08 | 2006-08-10 | Philip Jacoby | Beta-nucleation concentrates for film applications |
| CN101094884A (en) * | 2004-12-30 | 2007-12-26 | 3M创新有限公司 | Microporous materials and methods of making |
| TW201035113A (en) * | 2008-12-25 | 2010-10-01 | Sumitomo Chemical Co | Light diffuser plate |
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| EP2444453A4 (en) * | 2009-06-19 | 2012-12-12 | Mitsubishi Plastics Inc | Porous polypropylene film |
| CN103140544A (en) * | 2010-10-06 | 2013-06-05 | 三菱树脂株式会社 | Porous polyolefin resin film |
| WO2013002164A1 (en) * | 2011-06-29 | 2013-01-03 | 三菱樹脂株式会社 | Porous film, battery separator and battery |
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|---|---|---|---|---|
| CN101094884A (en) * | 2004-12-30 | 2007-12-26 | 3M创新有限公司 | Microporous materials and methods of making |
| US20060177632A1 (en) * | 2005-02-08 | 2006-08-10 | Philip Jacoby | Beta-nucleation concentrates for film applications |
| TW201035113A (en) * | 2008-12-25 | 2010-10-01 | Sumitomo Chemical Co | Light diffuser plate |
| CN103339176A (en) * | 2011-02-03 | 2013-10-02 | 东丽株式会社 | Porous polypropylene film, separator for electricity storage device, and electricity storage device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019238A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Polypropylene composition for lamps and preparation method thereof |
| CN111019238B (en) * | 2018-10-10 | 2022-12-27 | 中国石油化工股份有限公司 | Polypropylene composition for lamps and preparation method thereof |
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