KR101618980B1 - Olefin resin - Google Patents
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- KR101618980B1 KR101618980B1 KR1020140149266A KR20140149266A KR101618980B1 KR 101618980 B1 KR101618980 B1 KR 101618980B1 KR 1020140149266 A KR1020140149266 A KR 1020140149266A KR 20140149266 A KR20140149266 A KR 20140149266A KR 101618980 B1 KR101618980 B1 KR 101618980B1
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Abstract
Embodiments of the present application relate to a polyolefin resin having two crystallization temperatures, and it is possible to provide an encapsulant having high light transmittance and low haze value even under low lamination conditions, and the resin composition comprising the polyolefin resin can be used for various photoelectrons It is possible to provide an encapsulating material which is used in the production of an encapsulating material of the device and which has improved adhesion with the front substrate and the backsheet contained in the device, particularly long-term adhesive property and heat resistance.
Description
Embodiments of the present application are directed to olefin resins for optoelectronic device encapsulants.
BACKGROUND ART An optoelectronic device such as a photovoltaic cell, a light emitting diode (LED), or an organic light emitting diode (OLED) is an encapsulant for encapsulating a light emitting or photo- Encapsulant).
For example, a solar cell module is typically manufactured by laminating a transparent front substrate, a sealing material, a photovoltaic element, a sealing material, and a back sheet, which are light receiving substrates, .
Embodiments of the present application provide olefin resins for optoelectronic device encapsulants having novel properties.
One embodiment of the present application provides a polyolefin resin having two crystallization temperatures (Tc). For example, the polyolefin resin having the two crystallization temperatures can have excellent light transmittance and can be applied to various photovoltaic devices requiring excellent light transmittance, for example, an encapsulant for encapsulating elements of solar cells .
In the present application, "olefin resin" means a resin containing a polymer or copolymer derived from an olefin-based monomer, and does not include a resin blend. The term " polymer derived from a monomer " as used herein means a derivative of a monomer, for example, a polymer containing a polymerized unit of the monomer.
The term " crystallization temperature " as used herein means a temperature at which crystallization occurs in which the arrangement of the material structure, which is irregular, is regularly changed by attraction between molecules / atoms, occurs. For example, a differential scanning calorimetry DSC). ≪ / RTI >
In one example, the crystallization temperature is set to a temperature of 20 ° C / min in order to equalize the thermal history of the polyolefin resin while the measurement container is filled with a sample in an amount of about 0.5 mg to 10 mg and a nitrogen gas flow rate of 20 ml / The temperature was raised from 0 ° C to 200 ° C at a heating rate and maintained at that temperature for 2 minutes and then cooled to a temperature of -150 ° C at a rate of 10 ° C / ), That is, the exothermic peak temperature at the time of cooling can be measured as the crystallization temperature.
In the present specification, " peak " means the cooling curve or the vertex or vertex of a heating curve to be described later, for example, a point having a slope of tangent of zero. However, the point where the slope of the tangent line is not changed, that is, the inflection point is excluded, with respect to the point where the slope of the tangent line is 0, from among the points whose slant of the tangent line is zero.
The polyolefin resin according to one embodiment of the present application has two crystallization temperatures, for example, a first crystallization temperature of 20 캜 to 35 캜 and a second crystallization temperature higher than the first crystallization temperature. In one example, the polyolefin resin has a peak of a cooling curve of a heat flow amount measured by DSC while cooling at a rate of 10 ° C / min from a temperature of 200 ° C to -150 ° C, and a peak of a cooling curve of 20 ° C to 35 ° C and 35 ° C to 75 ° C Respectively. In this case, the peak appearing at 20 占 폚 to 35 占 폚 is the first crystallization temperature, and the peak at which the peak appears at 35 占 폚 to 75 占 폚 is the second crystallization temperature. Further, preferably, the polyolefin resin may have a first crystallization temperature of from 24 캜 to 33 캜 and a second crystallization temperature of from 40 캜 to 70 캜.
The difference between the first crystallization temperature and the second crystallization temperature may be at least 10 ° C, for example, at least 15 ° C. When the difference between the first crystallization temperature and the second crystallization temperature is too small, the light transmittance of the polyolefin resin can be reduced. The upper limit of the difference between the first crystallization temperature and the second crystallization temperature is not particularly limited, For example, 50 < 0 > C.
The polyolefin resin of the present application, a density of 0.850 g / cm 3 to 0.880 g / cm 3, e.g., 0.855 g / cm 3 to 0.870 g / cm 3, 0.859 g / cm 3 to 0.880 g / cm 3 Or 0.855 g / cm < 3 > to 0.877 g / cm < 3 >. In order to make the polyolefin resin have two crystallization temperatures, the density of the polyolefin resin can be controlled within the above range.
In one example, the crystallization temperature, as the density of the polyolefin resin increases, the polyolefin resin may have a high crystallization temperature. For example, when the density of the polyolefin resin is about 0.859 g / cm 3 to 0.862 g / cm 3 , the first crystallization temperature of the polyolefin resin is 23 ° C to 28 ° C, 45 ° C, or when the density of the polyolefin resin is about 0.875 g / cm 3 to 0.880 g / cm 3 , the first crystallization temperature of the polyolefin resin is 30 ° C to 35 ° C, 2 The crystallization temperature may be respectively at a temperature of 50 ° C to 67 ° C.
In the present application, it is also possible to provide a polyolefin resin having two crystallization temperatures and one melting temperature (Tm) as described above.
The term "melting temperature" refers to a temperature at which the polymer resin changes from a solid state to a liquid state having fluidity, and the temperature at which the flow of the crystallized portion of the resin starts, can be analyzed through the DSC described above.
For example, the melting temperature is measured by cooling the sample at a rate of 10 DEG C / min from a temperature of 200 DEG C to a temperature of -150 DEG C, measuring the crystallization temperature, and then heating the sample at -150 DEG C The peak of the heating curve of the heat flow measured by DSC, that is, the endothermic peak temperature at the time of heating can be measured as the melting temperature while raising the temperature to 200 ° C at a rate of 10 ° C / min.
The polyolefin resin according to one embodiment of the present application has a single melting temperature, for example, a heating curve of a heat flow rate measured by DSC while raising the temperature from -150 ° C to 200 ° C at a rate of 10 ° C / min May appear at a temperature of 40 캜 to 60 캜.
As the melt temperature, increase the density of the polyolefin resin, the polyolefin resin may have a high melting temperature, for example, the density of the polyolefin resin of about 0.859 g / cm 3 to 0.862 g / cm 3 il , The melting temperature of the polyolefin resin may appear at a temperature of 40 ° C to 45 ° C or when the density of the polyolefin resin is about 0.875 g / cm 3 to 0.880 g / cm 3 , the melting temperature of the polyolefin resin is Lt; RTI ID = 0.0 > 50 C < / RTI >
If the melting temperature is excessively high, the sealing material containing the polyolefin resin can not be laminated to the substrate at a low temperature, thereby raising the process temperature and increasing the cost. In view of this, The melting temperature can be controlled within the aforementioned range.
The polyolefin resin of the present application satisfies the following general formula (1).
[Formula 1]
10 ° C ≤ | Tc 2 -Tc 1 | - | Tm-Tc 2 | ≤ 20 ° C
In the
Tc 1 represents a first crystallization temperature,
Tc < 2 > represents a second crystallization temperature,
Tm represents the melting temperature.
When the polyolefin resin satisfies the general formula (1), the sealing material containing the polyolefin resin can be laminated to the substrate at a low temperature by adjusting the melting temperature so as not to be excessively high in relation to the crystallization temperature, The manufacturing process of the optoelectronic device can be efficiently performed.
In one example, the polyolefin resin of the present application has an ethylene content of from 0.1 g / 10 min to 20.0 g / 10 min., For example 0.5 g / 10 min., Under the conditions of ASTM D1238, 10.0 g / 10 min, 1.0 g / 10 min to 5.0 g / 10 min, 0.6 g / 10 min to 10.0 g / 10 min or 0.65 g / 10 min to 5.0 g / 10 min. When the MFR value is in the above range, for example, the resin composition described later can exhibit excellent moldability and the like. Such an MFR value can be measured, for example, under a load of 2.16 kg at 190 캜 for a polyolefin resin, but is not limited thereto.
In one example, the polyolefin resins having the two crystallization temperatures are derived from olefinic monomers and may include, for example, polymers or copolymers derived from the olefinic monomers. For example, the polyolefin resin having the two crystallization temperatures may be an ethylene / alpha-olefin copolymer, an ethylene polymer, or a propylene polymer, and in one embodiment may be an ethylene / alpha -olefin copolymer.
In one example, the olefinic monomer may be at least one monomer selected from the group consisting of ethylene, propylene and alpha -olefin-based monomers.
The? -Olefin-based monomer may be a branched? -Olefin-based monomer such as isobutylene; Butene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-phenyl- Butene, 3-methyl-1-butene, 4-methyl-1-butene, Linear? -Olefin-based monomers such as pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene and vinylcyclohexane; Hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene or 3,4- Halogen-substituted? -Olefin-based monomers such as butene; Or cyclic? -Olefin monomers such as cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene and 5-benzylnorbornene Etc., but the present invention is not limited thereto.
The polyolefin resin having two crystallization temperatures may be ethylene and an alpha -olefin-based monomer or a propylene-alpha-olefin-based monomer, and examples thereof include 1-butene, 1-hexene, Pentene, and 1-octene, and a copolymer of ethylene, preferably a copolymer of ethylene and 1-octene.
As used herein, the term " ethylene / alpha -olefin copolymer " means a polyolefin containing ethylene and alpha -olefin in a polymerized form as a main component and specifically includes at least 50 mol% or more of ethylene homopolymer May mean a copolymer containing ethylene as a polymerization unit and olefin monomers having three or more carbon atoms or other comonomers together as polymerized units.
The copolymer includes all the polymers having different configurations of the array even though they are prepared from the above-mentioned monomers. For example, in embodiments of the present application, in order to suitably control the viscosity or physical properties of the resin composition depending on the application, the arrangement of the copolymer included in the olefin resin may be randomly, crosswise, blockwise, And the copolymer may be a random copolymer of random type.
The ethylene /? - olefin copolymer may be, for example, a low density ethylene /? - olefin copolymer, a medium density ethylene /? - olefin copolymer, a high density ethylene /? - olefin copolymer, an ultra low density ethylene / , Ultra-low density ethylene /? - olefin copolymer, and linear low density ethylene /? - olefin copolymer.
The polyolefin resin having two crystallization temperatures of the present application is not particularly limited, and can be produced by polymerizing or copolymerizing the above-mentioned olefinic monomer in the presence of a catalyst. For example, the polyolefin resin can be produced by contacting an olefin-based monomer with a catalyst composition described below.
In one example, the polyolefin resins having the two crystallization temperatures can be prepared by polymerizing olefinic monomers in the presence of a nucleophilic catalyst.
The dinuclear catalyst may be a dinuclear metallocene compound having the following structure, and the binuclear metallocene compound is represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 to R 4 may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; Silyl radical; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; Or an arylalkyl radical having 7 to 20 carbon atoms; R 1 to R 4 Two or more adjacent groups may be connected to each other to form an aliphatic ring or an aromatic ring;
R 5 to R 7 may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical; The R 5 to R 7 Two or more adjacent groups may be connected to each other to form an aliphatic ring or an aromatic ring;
CY is an aliphatic or aromatic ring containing nitrogen and may be substituted or unsubstituted with halogen, an alkyl or aryl radical having 1 to 20 carbon atoms, and when the number of substituents is plural, two or more substituents in the substituent are connected to each other An aliphatic or aromatic ring;
M is a Group 4 transition metal;
X 1 is a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms;
n is an integer of 0 to 10;
Unlike a single active site catalyst, the above-mentioned dinuclear metallocene compound has a high accessibility to a substrate and can provide a catalyst having multiple active sites having high activity.
In the dinuclear metallocene compound of
The CY may be a pentagonal or hexagonal aliphatic or aromatic ring including nitrogen substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms, but is not limited thereto.
In addition, M may be titanium (Ti), zirconium (Zr), or hafnium (Hf), and X 1 may be halogen or an alkyl group having 1 to 20 carbon atoms, but is not limited thereto.
Examples of the binuclear metallocene compound represented by the above formula (1) include, but are not limited to, the following compounds.
In one example, the dinuclear metallocene compound represented by
The dinuclear metallocene compound represented by the formula (1) can be obtained by crosslinking two single metallocene compounds bridged with a phenylene group to which a cyclic amido group is introduced with an alkylenedioxy (-O- (CH 2 ) n O-) Structure. Therefore, the two metal centers are connected by a diether chain serving as a linker to reduce unnecessary interactions between the metals, thereby having a stable catalytic activity and being easy to deform the structure. The single active site catalyst , It is highly accessible and has high activity. Accordingly, when the above-described dinuclear metallocene compound is used as a catalyst in polyolefin polymerization or copolymerization, a polyolefin having a high molecular weight and a broad molecular weight distribution can be produced with high activity. Also, various substituents can be introduced into a cyclic amido ring such as cyclopentadienyl and quinoline or indolin, which ultimately makes it possible to easily control the electronic and stereoscopic environment around the metal. That is, by using a compound having such a structure as a catalyst, it is easy to control the structure and physical properties of the olefin polymer produced.
In the polymerization of olefinic monomers in the presence of the dinuclear catalyst of the novel structure as described above, a compound of the following
(2)
- [Al (R 8 ) -O] n -
In the general formula (2), R 8 is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, n is an integer of 2 or more,
(3)
D (R 9 ) 3
In Formula 3,
D is aluminum or boron, R < 9 > is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
[Chemical Formula 4]
[LH] + [ZA 4 ] - or [L] + [ZA 4 ] -
In Formula 4,
L is a neutral or cationic Lewis base, H is a hydrogen atom, Z is a
Examples of the compound represented by
Examples of the alkyl metal compound represented by Formula 3 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethyl Tri-n-butylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, Dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like can be used.
Examples of the compound represented by the general formula (4) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p (O, p-dimethylphenyl) boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, trimethylammoniumtetra (P-trifluoromethylphenyl) boron, tetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p -trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N , N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphor Tetramethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra (aluminum) (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl) Aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetrapenta Triphenyl aluminum, diethyl ammonium aluminum tetrapentafluorophenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl (P-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, dimethylphenylboronium tetraphenylboron, triphenylboronium tetraphenylboron, triphenylboronium tetraphenylboron, Anilinium tetrakis (pentafluorophenyl) borate, and the like.
The polyolefin resin can be produced by a solution process using the catalyst composition. In addition, when the catalyst composition is used together with an inorganic carrier such as silica, it can also be prepared by slurry or gas phase process.
In the solution process, the catalyst composition may be prepared by reacting an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane and isomers thereof and an aromatic hydrocarbon solvent such as toluene, Dichloromethane, chlorobenzene, or the like, or by dilution. The solvent used herein can be used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to further use a co-catalyst.
In particular, in the preparation of the polyolefin according to the present application, the catalytic composition can also carry out a copolymerization reaction of a monomer having a large steric hindrance such as ethylene and 1-octene. By using a dinuclear metallocene compound, the electronic and stereoscopic environment around the metal can be easily And ultimately it is possible to control the structure and physical properties of the produced polyolefin.
The polyolefin may be prepared using a continuously agitated reactor (CSTR) or a continuous flow reactor (PFR). The reactors may be arranged in series or in parallel, and may further include a separator for continuously separating the solvent and unreacted monomers from the reaction mixture.
In one example, when the polyolefin resin is subjected to a continuous solution polymerization process, the production process of the polyolefin resin may include a catalytic process, a polymerization process, a solvent separation process, and a recovery process as described below.
a) catalytic process
The catalyst composition can be injected by dissolving or diluting in an aliphatic or aromatic solvent having 5 to 12 carbon atoms which is unsubstituted or substituted with halogen suitable for the olefin polymerization process. For example, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof, aromatic hydrocarbon solvents such as toluene, xylene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene Can be used. The solvent used herein can be used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum or the like, or it can be carried out by using an excessive amount of cocatalyst.
b) Polymerization process
The polymerization process can be carried out by introducing at least one olefinic monomer and a catalyst composition comprising a dinuclear metallocene compound of formula (1) and a cocatalyst on the reactor. In the case of solution phase and slurry polymerization, the solvent is injected onto the reactor. In the case of solution polymerization, a mixture of a solvent, a catalyst composition and a monomer is present in the reactor.
The molar ratio of the monomer to the solvent suitable for the reaction may be adjusted in consideration of the ratio suitable for dissolving the raw material before the reaction and the polymer produced after the reaction. For example, the molar ratio of monomer to solvent may be from 10: 1 to 1: 10,000, from 5: 1 to 1: 100, or from 1: 1 to 1: 2. If the amount of the solvent is too small, the viscosity of the fluid may increase, resulting in a problem of transferring the resulting polymer. If the amount of the solvent is excessively large, the amount of the solvent is excessively large, The amount of the solvent can be appropriately controlled within the above-mentioned range in consideration of this point.
The solvent may be introduced into the reactor using a heater or a freezer at a temperature of -40 ° C to 150 ° C, thereby initiating the polymerization reaction with the monomer and the catalyst composition. Generally, when the temperature of the solvent is too low, the reaction temperature may be lowered in accordance with the amount of the reaction. In this case, if the temperature of the solvent is too high, it is difficult to remove the reaction heat due to the reaction The temperature of the solvent can be adjusted to the above-mentioned range in consideration of this point.
Also, by introducing feeds (solvents, monomers, catalyst compositions, etc.) by elevating the pressure to above 50 bar, a high capacity pump can provide a mixture of the feeds without additional pumping between the reactor arrangement, .
The internal temperature of the reactor, that is, the polymerization reaction temperature may be adjusted to -15 ° C to 300 ° C, for example, 50 ° C to 200 ° C, or 50 ° C to 150 ° C. If the internal temperature is too low, the reaction rate is low and the productivity is low. If the internal temperature is too high, there may occur a problem of discoloration such as generation of impurities due to side reactions and carbonization of the polymer. The internal temperature of the reactor can be adjusted within the above-mentioned range.
The internal pressure of the reactor can be controlled from 1 bar to 300 bar, for example from 30 to 200 bar, or from 30 to 50 bar. If the internal pressure is excessively low, the reaction rate is low, resulting in low productivity, and there is a problem due to vaporization of the solvent used. If the internal pressure is excessively high, there is a problem of equipment cost such as equipment cost due to high pressure. The pressure inside the reactor can be controlled within the above-mentioned range.
The polymer produced in the reactor may be maintained at a concentration of less than 20 wt% in the solvent and may be transferred to the first solvent separation process for solvent removal after a short residence time. The residence time in the reactor of the resulting polymer can be from 1 minute to 10 hours, for example from 3 minutes to 1 hour, or from 5 minutes to 30 minutes. When the residence time is too short, there is a problem such as a decrease in productivity due to a short residence time, a loss of catalyst, and an increase in manufacturing cost. In case of an excessively long residence time, Therefore, the residence time in the reactor can be adjusted within the above-mentioned range in consideration of this point.
c) solvent separation process
The solvent may be separated by varying the solution temperature and pressure for removal of the solvent present with the polymer exiting the reactor. For example, the polymer solution transferred from the reactor is heated from about 200 ° C to 230 ° C through a heater, and then the pressure is lowered through the pressure drop device. In the first separator, the unreacted raw material and the solvent can be vaporized.
The pressure in the separator can then be adjusted from 1 to 30 bar, for example from 1 to 10 bar, or from 3 to 8 bar. If the pressure in the separator is excessively low, the content of the polymer is increased and there is a problem in transferring. In case where the pressure is too high, it is difficult to separate the solvent used in the polymerization process. Therefore, Can be adjusted.
In addition, the temperature in the separator can be adjusted from 150 캜 to 250 캜, for example, from 170 캜 to 230 캜, or from 180 캜 to 230 캜. If the temperature in the separator is too low, there is a problem in transporting the copolymer and its mixture due to increased viscosity. In case of excessively high temperature, there is a problem of discoloration due to carbonization of the polymer due to denaturation at high temperature. , The temperature in the separator can be adjusted within the range described above.
The solvent vaporized in the separator can be recycled to the condensed reactor in the overhead system. When the first stage solvent separation process is carried out, a concentrated polymer solution of up to 65% can be obtained. The polymer solution concentrated to 65% is transferred to the second separator by the transfer pump through the heater, and the separation process for the residual solvent proceeds in the second separator. In order to prevent the polymer from being deformed due to high temperature while passing through the heater, a heat stabilizer may be added. In order to suppress the reaction of the polymer due to the residual activity of the active substance present in the polymer solution, It can be injected into the heater together. The residual solvent in the polymer solution injected into the second separator is finally completely removed by a vacuum pump, and a granulated polymer can be obtained after passing through the cooling water and the cutter. In the second separation process, the gasified solvent and other unreacted monomers can be reused after purification through a recovery process.
d) Recovery process
The organic solvent added with the raw material to the polymerization process may be recycled to the polymerization process together with the unreacted raw material in the primary solvent separation process. However, since the solvent recovered in the secondary solvent separation process contains a large amount of moisture acting as a catalyst poison in the solvent due to contamination due to incorporation of a reaction inhibitor to stop the catalytic activity and steam supply in the vacuum pump, It is preferable to be reused after purification.
The olefin resin having two crystallization temperatures prepared by the above method may be contained in a resin composition for producing an encapsulant for an optoelectronic device and the resin composition containing the olefin resin An encapsulant for an optoelectronic device including a modified olefin resin produced by extrusion has not only excellent adhesive strength but also high light transmittance and low haze value even when laminated at a low temperature.
In the present specification, the "modified olefin resin" and "modified ethylene / -olefin copolymer" have the same meaning as the copolymer including the branch represented by the following formula (7). In order to distinguish the modified olefin resin or the modified ethylene /? - olefin copolymer from the above-mentioned modified olefin resin or modified ethylene /? - olefin copolymer, the ethylene /? - olefin copolymer grafted only with the unsaturated silane compound without the presence of the aminosilane compound is referred to as " Quot; silane-modified ethylene / alpha -olefin copolymer ".
In one example, the resin composition may further include an unsaturated silane compound and a radical initiator, in addition to the olefin resin having two crystallization temperatures of the present invention described above.
The unsaturated silane compound contained in the resin composition is an unsaturated silane compound represented by the following formula (5). The unsaturated silane compound is grafted to the main chain containing a polymerization unit of an olefin-based monomer in the presence of a radical initiator and the like, A resin or a silane-modified olefin resin can be produced. For example, the resin composition may be subjected to reactive extrusion to produce a silane-modified olefin resin grafted with an unsaturated silane compound represented by the following general formula (5) to the olefin resin.
[Chemical Formula 5]
DSiR 10 p R 11 (3-p)
In Formula 5, D represents alkenyl bonded to a silicon atom. The alkenyl means a functional group having at least one unsaturated group such as a double bond, and the number of carbon atoms of the alkenyl may be 2 to 20, 2 to 12, or 2 to 6. The alkenyl may be, for example, vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl or gamma-methacryloxypropyl, and the like.
R 10 represents a hydroxyl group, halogen, an amine group or -R 12 R 13 bonded to a silicon atom, R 12 represents an oxygen or sulfur atom, R 13 represents an alkyl group, an aryl group or an acyl group, R 11 represents a silicon atom An alkyl group, an aryl group or an aralkyl group,
In one example, may be a reactive functional group that can be hydrolyzed by the approach of the water present in the R 10 is type, wherein R 10 is, for example, an alkoxy group, an alkylthio group, an aryloxy group, an acyloxy A halogen group, or an amine group. Examples of the alkoxy group in this case include an alkoxy group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms and 1 to 4 carbon atoms, examples of the acyloxy group include a C1-C12, Or an acyloxy group having 1 to 4 carbon atoms. Examples of the alkylthio groups include alkylthio groups having 1 to 12 carbon atoms, 1 to 8 carbon atoms, and 1 to 4 carbon atoms.
In one embodiment, R 10 in Formula 5 may be an alkoxy group, specifically, an alkoxy group having 1 to 12 carbon atoms or 1 to 8 carbon atoms, and in other embodiments, 1 to 4 carbon atoms An alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group or a butoxy group, and for example, a methoxy group or an ethoxy group may be used in some embodiments.
The R 11 may be a non-reactive functional group. For example, R 11 may be hydrogen, an alkyl group, an aryl group, or an aralkyl group. The alkyl group may be, for example, an alkyl group having 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The aryl group may be an aryl group having 6 to 18 carbon atoms or 6 to 12 carbon atoms such as a phenyl group, and the aralkyl group may be an aralkyl group having 7 to 19 carbon atoms or 7 to 13 carbon atoms such as a benzyl group have
In Formula 5, p is an integer of 1 to 3, and may be 3 in some embodiments.
A specific example of the unsaturated silane compound of Formula 5 may be vinylalkoxysilane. For example, the unsaturated silane compound may be selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentoxysilane, vinyltriphenoxy Silane, vinyltriacetoxysilane, and the like. Among them, vinyltrimethoxysilane or vinyltriethoxysilane can be used, but the present invention is not limited thereto.
In one example, the resin composition may contain 0.1 to 10.0 parts by weight, 0.5 to 7.0 parts by weight, 1.0 to 5.5 parts by weight, or 0.5 to 5 parts by weight, based on 100 parts by weight of the total resin composition, of the unsaturated silane compound of Formula 5, 5.0 parts by weight. Within this range, the adhesiveness of the silane-modified olefin resin, for example, adhesion to a glass substrate, a backsheet, and the like can be kept excellent.
Unless otherwise specified, unit weight parts in the present specification means weight ratios.
In one example, the resin composition may comprise a radical initiator. The radical initiator may serve to initiate a reaction in which the unsaturated silane compound is grafted to the olefin resin.
The radical initiator is not particularly limited as long as it can initiate the radical polymerization of the vinyl group, and examples thereof include one or more selected from the group consisting of organic peroxides, hydroperoxides and azo compounds. Specific examples thereof include t-butylperoxyperoxide, di-t-butylperoxide, di-cumylperoxide, 2,5-dimethyl-2,5-di (t- butylperoxy) Dialkyl peroxides such as 2,5-di (t-butylperoxy) -3-hexyne; Hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-di (hydroperoxy) hexane, and t-butyl hydroperoxide; Diacyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide and 2,4-dichlorobenzoyl peroxide; butyl peroxy isobutyrate, t-butyl peroxyacetate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyoctoate, t- Butyl peroxybenzoate, di-t-butylperoxy phthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl- (Benzoyl peroxy) -3-hexyne; And ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, azo compounds such as lauryl peroxide, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile) , But the present invention is not limited thereto.
The radical initiator may be included in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the total resin composition.
In one example, the resin composition may further include an aminosilane compound in addition to the unsaturated silane compound. The aminosilane compound may be used in the grafting denaturation step of the olefin resin, for example, the ethylene / alpha -olefin copolymer And functions as a catalyst for promoting the hydrolysis reaction of converting a reactive functional group such as an alkoxy group of an unsaturated silane compound grafted to the olefin resin into a hydroxyl group to improve the adhesion strength with the backsheet composed of the upper and lower glass substrates or the fluororesin . At the same time, the aminosilane compound is also involved as a reactant in a direct copolymerization reaction, thereby providing a moiety having an amine functional group in the modified olefin resin.
The aminosilane compound may be a compound represented by the following general formula (6).
[Chemical Formula 6]
SiR 14 q R 15 (4-q)
In the above formula (6), R 14 represents - (CH 2 ) r NR 16 R 17 bonded to a silicon atom, R 16 and R 17 each independently represent hydrogen or R 18 NH 2 bonded to a nitrogen atom , And R 18 represents alkylene having 1 to 6 carbon atoms.
R 15 is a halogen atom bonded to a silicon atom, an amine group -R 19 R 20 Or -R 20 , R 19 is an oxygen or sulfur atom, and R 20 represents hydrogen, an alkyl group, an aryl group, an aralkyl group or an acyl group.
In this case, q is an integer of 1 to 4, and r is an integer of 0 or more.
In the above, the alkyl group, aryl group, aralkyl group, acyl group and alkylene are the same as described above, and a description thereof will be omitted.
Preferably, in Formula 6, R 15 is -R 19 R 20 (CH 2 ) r NR 16 R 17 in which R 19 is an oxygen atom, R 20 is hydrogen, an alkyl group, an aryl group, an aralkyl group or an acyl group and R 14 is a silicon atom, R 16 And R 17 may be hydrogen, or R 16 may represent hydrogen and R 17 may represent R 18 NH 2 , wherein R 18 may be alkylene having 1 to 3 carbon atoms. In this case, r may be an integer of 2 to 5.
The aminosilane compound may be added at the stage of denaturation of the olefin resin, that is, at the stage of producing the modified olefin resin.
In addition, the aminosilane compound can stably maintain the overall properties of the composition as intended, without adversely affecting other components contained in the composition, for example, a UV stabilizer as described later.
The compound usable as the aminosilane compound is not particularly limited as long as it is a primary amine or a secondary amine, and is a silane compound containing an amine group. For example, aminotrialkoxysilane, aminodialkoxysilane and the like can be used as the aminosilane compound, and examples thereof include 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane Aminopropyltriethoxysilane (APTES), bis [(3-triethoxysilyl) propyl] amine, bis [(3-trimethoxysilyl) propyl] amine, 3-aminopropylmethyldiethoxysilane, Dimethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine (DAS), aminoethylaminopropyltriethoxysilane, aminoethylaminopropylmethyldimethylamine Aminoethylaminomethyltriethoxysilane, aminoethylaminomethylmethyldiethoxysilane, diethylenetriaminopropyltrimethoxysilane, diethylenetriaminopropyltriethoxysilane, diethylenetriaminopropyltriethoxysilane, diethylenetriaminopropyltriethoxysilane, (N-phenylamino) methyltriethoxysilane, (N-phenylamino) methyltrimethoxysilane, (N-phenylamino) methyltrimethoxysilane, (N-phenylamino) propyltrimethoxysilane, 3- (N-phenylamino) propyltrimethoxysilane, 3- (N-phenylamino) propylmethyldimethoxysilane, 3- (N-phenylamino) propylmethyldiethoxysilane and N- (N-butyl) -3-aminopropyltrimethoxysilane. More than species. The aminosilane compound may be used alone or in combination.
0.01 to 0.5 parts by weight, 0.1 to 0.25 parts by weight, 0.2 to 0.5 parts by weight, 0.5 to 1.25 parts by weight, 0.1 to 1.5 parts by weight of the aminosilane compound may be contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the total resin composition. Or 0.2 to 2.0 parts by weight. In this weight ratio, the physical properties of the resin composition can be effectively controlled, the adhesive strength to the front substrate and the back sheet can be increased, and the activity of other additives contained in the resin composition can be kept excellent. If the content of the aminosilane compound to be added is excessive, discoloration of the resin may occur prematurely or a large amount of gel may be formed during the process, thereby adversely affecting the appearance of the sheet to be produced.
The aminosilane compound is used in an amount of 1 to 35 parts by weight, for example, 2 to 6 parts by weight, 2 to 5.5 parts by weight, 5 to 5.5 parts by weight, and 2 to 15 parts by weight, based on 100 parts by weight of the unsaturated silane compound in the total resin composition 5 to 15 parts by weight, 10 to 35 parts by weight, 5 to 35 parts by weight, 15 to 33.3 parts by weight or 2 to 33.3 parts by weight of the total amount of the
The aminosilane compound and the unsaturated silane compound are similar in terms of the silyl group but are different in that they each contain an amine functional group and have an unsaturated group. For example, both the aminosilane compound and the unsaturated silane compound may include both materials, , It is possible to provide excellent adhesion performance as compared with the case where only one of the two materials is contained. Here, the addition of the aminosilane compound may improve the bonding performance absolutely irrespective of the content of the unsaturated silane compound. However, even when the unsaturated silane compound of the same content is used, Can be improved.
Further, according to the embodiments of the present application, it is possible to provide an encapsulant having an adhesive property remarkably superior to that in the case where an encapsulant is simply produced using an alkylsilane or an alkylamine. For example, in the case of using only alkylamine, unlike vinylsilane or aminosilane compound, the alkylamine does not participate in the grafting polymerization reaction and remains as a material remaining in the system, and then moves to the surface of the modified olefin resin Or moved to the surface of the sheet during production with a sheet-like encapsulant. Therefore, the long term durability is deteriorated due to the materials remaining in the system. Further, in the case of some alkyl amines, there is a problem that the melting point is about 27 to 29 캜 and the miscibility with other reactants, for example, a liquid silane compound is poor at a temperature range lower than the melting point.
The resin composition may further include at least one additive selected from a light stabilizer, a UV absorber, a heat stabilizer and the like, if necessary.
The light stabilizer may act to prevent photo-oxidation by capturing the active species of the initiation of photo-initiation of the olefin resin according to the application to which the composition is applied. The type of light stabilizer that can be used is not particularly limited, and for example, a known compound such as a hindered amine compound or a hindered piperidine compound can be used.
The UV absorber can act to absorb ultraviolet rays from sunlight or the like and convert it into harmless thermal energy in the molecule to prevent excitation of the active species of photo-initiation initiation in the olefin resin, depending on the use of the composition . The specific kind of the UV absorber that can be used is not particularly limited and includes, for example, inorganic UV such as benzophenone, benzotriazole, acrylonitrile, metal complex salt, hindered amine, ultrafine titanium oxide, Absorbing agent and the like, or a mixture of two or more thereof.
Examples of the heat stabilizer include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diyl bisphosphonate and bis (2,4-di-tert- butylphenyl) pentaerythritol diphosphite Of thermal stabilizers; And a reaction product of 8-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene, and one or more of the above- have.
In the resin composition, the content of the light stabilizer, the UV absorber and / or the heat stabilizer is not particularly limited. That is, the content of the additive can be appropriately selected in consideration of the use of the resin composition, the shape and the density of the additive, and can be appropriately adjusted within the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin composition have.
In addition to the above components, the exemplary resin composition may suitably further include various additives known in the art depending on the application to which the resin component is applied.
Still another embodiment of the present application can provide a method for producing an encapsulant for an optoelectronic device by using the resin composition and an encapsulant for an optoelectronic device manufactured by the method.
In one example, the method for producing the encapsulant for optoelectronic devices may comprise the step of producing a modified olefin resin.
The method for producing the modified olefin resin is not particularly limited. For example, the resin composition containing the olefin resin and the unsaturated silane compound having two crystallization temperatures of the present application or the olefin resin having two crystallization temperatures of the present application, An unsaturated silane compound and an aminosilane compound is prepared, mixed in a reactor, and subjected to a grafting extrusion reaction through heating and melting in the presence of an appropriate radical initiator.
The type of the reactor in which the modified olefin resin is produced is not particularly limited as long as it can produce a desired resin by reacting reactants in a heat-fused or liquid state. For example, the reactor may be an extruder or an extruder with a hopper. In the case of using such a reactor, for example, an olefin resin, a radical initiator, an aminosilane, an aminosilane, an aminosilane compound and a radical initiator may be added to the olefin resin heated and melted through an extruder, A compound and an unsaturated silane compound are mixed and added, followed by heating and melting in an extruder to cause a reaction to produce a modified olefin resin.
Other additives such as an ultraviolet absorber, a heat stabilizer or a UV stabilizer may be added to the modified olefin resin prepared as described above, and the additives may be added into the reactor before or after the modified olefin resin is formed. For example, the process may be simplified by simultaneously producing the modified olefin resin and mixing with additives in one reactor.
Other additives may be introduced into the reactor as they are, or they may be mixed in the form of a master batch and mixed. The master batch means a pellet-shaped raw material in which additives to be added are concentrated and dispersed at a high concentration. In general, when a plastic raw material is processed by a method such as extrusion or injection, Is used to introduce additives.
The method for introducing the additive into the reactor in which the modified olefin resin is formed is not particularly limited. For example, a side feeder may be installed at an appropriate position of the extruder or the cylinder, A method of adding an additive or a method of mixing with an olefin resin or the like in a hopper and inputting the mixture may be used.
In the above method, the conditions such as the specific kind and design of the reactor, the heating and melting, the mixing or the reaction, the conditions such as the temperature and the time, and the production method of the master batch are not particularly limited and may be suitably selected in consideration of raw materials to be used have.
Further, the encapsulating material film for an optoelectronic device can be produced by molding the resin composition into a film or a sheet form. Such a molding method is not particularly limited, and it is possible to produce an encapsulating material by sheeting or filming by a conventional process such as a T-die process or extrusion. Embodiments of the present application can be carried out by an in situ process using an apparatus in which the above-described modified olefin resin, a resin composition containing the same, and a film or sheet process are connected to each other .
The encapsulant for optoelectronic devices includes a reactive extrudate of a resin composition comprising an olefin resin having the two crystallization temperatures described above. Thus, in the encapsulating material, the temperature is raised or lowered at a temperature of -120 캜 to 600 캜, The peaks of the heating or cooling curve of the heat flux measured at 20 ° C to 35 ° C and 35 ° C to 75 ° C, respectively. In this case, the peak at 20 占 폚 to 35 占 폚 is the first crystallization temperature, and the peak at 35 占 폚 to 75 占 폚 is the second crystallization temperature. Further, preferably, the sealing material may have a first crystallization temperature of 24 캜 to 33 캜 and a second crystallization temperature of 40 캜 to 70 캜. The above-mentioned " reaction extrudate " means a modified olefin resin or a silane-modified olefin resin prepared by reacting the resin composition in an extrusion reactor.
In addition, the sealing material is produced using the resin composition comprising the polyolefin resin having the two crystallization temperatures described above, so that the sealing material exhibits excellent optical characteristics with high light transmittance and low haze even when it is produced by lamination at a low lamination temperature.
For example, the encapsulant film satisfies the following general formula (2).
[Formula 2]
Tt ≥ 91.0%
In the
Further, the sealing material film may satisfy the following general formula (3).
[Formula 3]
Hz? 4.6%
In the general formula (3), Hz represents the haze measured by a haze meter after laminating the sealing film to a glass substrate at a temperature of 110 ° C.
The total light transmittance and haze are values measured with a haze meter for light having a wavelength of 200 nm or more, for example, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm or 600 nm And may be a value measured with a haze meter, preferably for light at a wavelength of 550 nm. The total light transmittance and haze of the encapsulating film of the present invention measured above are the total light transmittance and the haze value of the laminate laminated with the encapsulating material on the glass substrate and the glass substrate and the encapsulating material film are laminated through a vacuum laminator .
Also, the total light transmittance can be measured using UV / Vis spectroscopy. In this case, the total light transmittance is a value measured using UV / Vis spectroscopy for light having a wavelength of 200 nm or more, for example, light having a wavelength of 200 to 1300 nm, 250 to 1300 nm, or 300 to 1100 nm .
The total light transmittance of the encapsulant film is preferably not less than 91.0%, for example, not less than 91.2%, not less than 91.3%, not less than 91.5%, not less than 91.7%, after laminating the encapsulant film to a glass substrate at a temperature of 110 캜 Or 91.9% or more, and can be adjusted to have the total light transmittance in the above-mentioned range in consideration of the photoelectric efficiency of the optoelectronic device.
The haze of the encapsulant film may be measured at a temperature of 110 ° C after laminating the encapsulant film to a glass substrate. The measured value is 4.6% or less, for example 4.0% or less, 3.5% or less, 3.0% Or less, or 2.0% or less, or 1.5% or less, and can be adjusted to have a haze value within the above-mentioned range in consideration of the photoelectric efficiency of the optoelectronic device.
In the present application, it is possible to provide a copolymer to be described later, that is, a modified olefin resin prepared by reactive extrusion using the above-mentioned production method using the above-mentioned reactive extrudate of the resin composition, for example, the resin composition, The coalescence may be included, for example, in the encapsulant for the optoelectronic device. The above-mentioned modified olefin resin exhibits excellent optical properties with high light transmittance and low haze by containing the above-mentioned olefin resin having two crystallization temperatures in a polymerized form.
In one example, the copolymer comprises a main chain comprising polymerized units of an olefinic monomer; And a branch bonded to the main chain and represented by the following formula (7).
(7)
-SiR < 21 & gt; R < 22 > (3-a)
In Formula 7,
R 21 and R 22 each independently represent a halogen atom bonded to a silicon atom, an amine group, -R 23 R 24 Or -R 24 , R 23 is an oxygen or sulfur atom, R 24 is hydrogen, an alkyl group, an aryl group, an aralkyl group or an acyl group, and a is an integer of 1 to 3.
Preferably, in Formula 7, R 21 and R 22 each independently represent -R 23 R 24 bonded to a silicon atom, R 23 represents oxygen, and R 24 represents hydrogen or an alkyl group.
In one example, the copolymer may further include a branched chain bonded to the main chain and represented by the following formula (8).
[Chemical Formula 8]
-SiR 25 b R 26 (2-b) R 27
In the formula (8), R 25 and R 26 each independently represent a halogen, an amine group, -R 28 R 29 or -R 29 bonded to a silicon atom, R 28 represents an oxygen or sulfur atom, and R 29 represents a hydrogen , An alkyl group, an aryl group, an aralkyl group or an acyl group, b is an integer of 1 or 2,
R 27 represents -OSiR 30 c R 31 (2-c) R 32 bonded to a silicon atom,
R 30 And R 31 each independently represents a halogen, an amine group bonded to a silicon atom, -R 33 R 34 or -R 34 , R 33 is an oxygen or sulfur atom, and R 34 is hydrogen, an alkyl group, an aryl group, Lt; RTI ID = 0.0 >
R 32 represents - (CH 2 ) d NR 35 R 36 bonded to a silicon atom, R 35 and R 36 each independently represents hydrogen or R 37 NH 2 bonded to a nitrogen atom, and R 37 represents an alkyl R,
C is an integer of 1 or 2, and d is an integer of 0 or more.
The copolymer may include, for example, a branch represented by the formula (7) grafted onto a main chain containing a polymerization unit of an olefin-based monomer, and may further include a branch represented by the formula (8) When the branch represented by the general formula (8) is further included, it may have a structure including a moiety in which a hydrocarbon group of some silyl group is converted into a hydroxy group, and a moiety having an amine functional group is also included. By including not only the moiety in which the copolymer is converted into a hydroxyl group but also an amine functional group, for example, a hydrogen bond is formed between the hydroxyl group and the amine functional group on the glass substrate surface under the encapsulating material in the optoelectronic device, And can form more hydrogen bonds with the backsheet made of the fluororesin on the top of the sealing material, and can provide excellent bonding strength.
In one example, the number of carbon atoms of the alkyl group in the general formulas (7) and (8) may be 1 to 20, 1 to 12, 1 to 8 or 1 to 4, and may be, But is not limited thereto.
In the general formulas (7) and (8), the number of carbon atoms of the aryl group may be 6 to 20, 6 to 18, or 6 to 12, for example, a phenyl group or a naphthyl group.
In the general formulas (7) and (8), the aralkyl group means an alkyl group in which at least one hydrogen atom of the hydrocarbon group of the alkyl group is substituted by an aryl radical, and the number of carbon atoms of the aralkyl group is 7 to 40, 7 to 19, or 7 to 13 Lt; / RTI > The carbon number of the aralkyl group means the total number of carbon atoms contained in the alkyl group and the aryl radical.
In the general formulas (7) and (8), the alkylene group may be a linear or branched alkylene group having 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 6 carbon atoms or 1 to 4 carbon atoms, for example, an ethylene group or a propylene group But is not limited thereto.
The acyl group in the above general formulas (7) and (8) is a functional group represented by RC = O, wherein R represents an alkyl group or an aryl group and includes, for example, formyl, acetyl, propionyl or benzoyl . The number of carbon atoms of the alkyl group and the aryl group contained in the acyl group is the same as described above,
In one example, in Formula 8, R 25 and R 26 May be a reactive functional group that can be hydrolyzed by the approach of water present in the system, and the description thereof is omitted for the same reason as the above-described reactive functional group.
The R 25 or R 26 may be a non-reactive functional group, and the same explanation as the above-mentioned non-reactive functional group will be omitted.
In the above formula (8), R 27 is a functional group containing a moiety having a hydroxy group converted to the above-mentioned hydroxy group and a moiety having an amine functional group, through which the copolymer of the present application is immobilized, A hydrogen bond is formed between the hydroxyl group and the amine functional group on the surface of the glass substrate of the sealing substrate to provide a more excellent bonding strength and a more hydrogen bond is formed with the backsheet made of the fluororesin on the sealing material, .
In one example, preferably, in the above formula (8), R 25 and R 26 each independently represent a hydroxy group bonded to a silicon atom or -R 28 R 29 , R 28 is oxygen, R 29 is an alkyl group , R 27 represents -OSiR 30 c R 31 (2-c) R 32 bonded to a silicon atom, R 30 And R 31 each independently represents a hydroxy group or -R 33 R 34 bonded to a silicon atom, R 33 represents oxygen, R 34 represents an alkyl group, and R 32 represents a - (CH 2 ) d NR 35 R 36 , R 35 and R 36 each independently represent hydrogen or R 37 NH 2 bonded to a nitrogen atom, and R 37 may represent alkylene.
More preferably, in the above formula (8), R 25 and R 26 represent a hydroxyl group, R 27 represents -OSiR 30 c R 31 (2-c) R 32 bonded to a silicon atom, and R 30 And R 31 represents a hydroxyl group, R 32 represents - (CH 2 ) d NR 35 R 36 bonded to a silicon atom, R 35 represents hydrogen, R 36 represents R 37 NH 2 , and R 37 represents an alkylene Lt; / RTI >
The alkyl group and alkylene in the above are the same as described above.
As described above, when the modified olefin resin, that is, the copolymer includes not only a moiety converted to a hydroxyl group but also an amine functional group, a copolymer containing the moiety represented by the above formula (7), for example, Only the unsaturated silane compound having a vinyl group in the olefin resin can be converted at a very high rate to convert a part of the hydrocarbon group of the silyl group to the hydroxyl group as compared with the copolymerized copolymer, that is, the silane modified olefin resin. Thus, when the modified olefin resin is included in the encapsulant of the optoelectronic device, the hydrogen bond between the hydroxyl group and the amine functional group on the surface of the glass substrate under the encapsulating material is lower than that of the silane-modified olefin resin containing the More adhesive strength can be provided, and more hydrogen bonds can be formed with the backsheet made of the fluororesin on the top of the sealing material, so that excellent adhesive strength can be provided.
The copolymer may be used as an encapsulant for encapsulating an element in various optoelectronic devices, but is not limited thereto. For example, the copolymer may be used as an industrial material applied to a heating lamination process or the like.
In one example, the encapsulant for optoelectronic devices includes a modified olefin resin prepared by grafting a resin composition according to the present application, that is, the above-mentioned copolymer. As described above, the copolymer contains branch (s) of the general formulas (7) and (8), whereby a part of the silyl group in which the hydrocarbon group is converted into the hydroxyl group and the part All included. The silane-modified moiety (A) with an amine group and the silane-modified moiety (B) may have a ratio of 99: 1 to 40:60.
The encapsulant for the optoelectronic device may include a non-modified olefin resin other than the modified olefin resin. The specific type of non-modified olefin resin that can be used is not particularly limited. For example, as the non-modified olefin resin, polyethylene may be used. Specifically, an ethylene /? - olefin copolymer belonging to the same category as the ethylene /? - olefin copolymer used in the production of the modified olefin resin Can be used.
The content ratio of the non-modified olefin resin and the modified olefin resin may be 1: 1 to 20: 1. If the amount of the unmodified olefin resin is too large, the adhesion performance expressed by the modified olefin resin tends to deteriorate. If the amount of the unmodified resin is too small, the adhesion performance expressed by the modified olefin resin develops early, So that the sheet formability may be undesirable.
The content of the non-modified olefin resin is not particularly limited and may be selected in consideration of desired physical properties. For example, the non-modified olefin resin may be contained in an amount of 0.01 to 3,000 parts by weight, 100 to 2000 parts by weight, or 90 to 1000 parts by weight based on 100 parts by weight of the modified olefin resin .
The encapsulation material may be contained in a state in which the respective components are uniformly mixed in the state, or may be contained in a state of being molded by various molding methods such as hot melt extrusion and T-die molding.
The shape of the sealing member is not particularly limited, and may be, for example, a sheet or a film. In this case, the thickness of the encapsulating material can be adjusted to about 10 탆 to 2,000 탆, or about 100 탆 to 1250 탆, in consideration of the supporting efficiency of the device, the possibility of breakage, the weight of the device, However, the thickness of the encapsulant may vary depending on the specific application to which it is applied.
An encapsulant made from the resin composition can be used in an optoelectronic device including an encapsulated optoelectronic device.
The optoelectronic component that is encapsulated may be a light emitting or light sensing part, such as a photovoltaic cell, a light emitting diode or an organic light emitting diode, for example.
The specific structure of the optoelectronic device or the method of encapsulating the optoelectronic device using the resin composition described above is not particularly limited and may be applied according to the purpose according to the device.
For example, when the optoelectronic device is a photovoltaic device, the optoelectronic device may include a
Such a solar cell module is manufactured by a usual molding method such as a lamination method in which a front substrate, an encapsulant, a photovoltaic element, a backsheet, etc. are laminated in accordance with a desired structure and then heated and pressed while being vacuum- can do. In this case, the processing conditions of the lamination method are not particularly limited and can be generally carried out at a temperature of 90 to 230 캜, or 110 to 200 캜 for 1 to 30 minutes, or 1 to 10 minutes.
In the case of the above-mentioned resin composition, the reactive silyl group of the silane-modified moiety of the chemically unstable modified olefin resin, for example, methoxysilyl group (Si-O-CH 3 ) The hydrolysis is promoted by the aminosilane compound to be converted into a silanol group (Si-OH), and a chemical covalent bond is formed by dehydration condensation with residues such as a hydroxyl group on the front substrate surface of the optoelectronic device, Lt; / RTI >
In addition, fluorine and silanol groups form a hydrogen bond even at the interface with the backsheet having a surface layer containing a fluoropolymer which is frequently used in recent years, so that high interfacial adhesion can be exhibited unlike conventional sealing materials. In addition, the non-covalent bonding site with fluorine is increased by a moiety having an amine functional group introduced by a small amount of an aminosilane compound, so that a high bonding strength can be provided.
The specific types of the front substrate, the back sheet, and the photovoltaic device that can be used in the above are not particularly limited. For example, the front substrate may be a conventional plate glass; Or a transparent composite sheet obtained by laminating a glass, a fluororesin sheet, a weather resistant film and a barrier film, and the back sheet may be a composite sheet comprising a metal such as aluminum, a fluororesin sheet, a weather resistant film and a barrier film, And a surface layer containing a polymer. For example, it may be a multilayer film in which a fluoropolymer layer is formed on both sides of a polyethylene terephthalate (PET) film. The photovoltaic device may be, for example, a silicon wafer type active layer or a thin film active layer formed by chemical vapor deposition (CVD) or the like.
In embodiments of the present application, it is possible to provide a polyolefin resin capable of providing an encapsulant having high light transmittance and a low haze value even under a low lamination condition, and the resin composition comprising the polyolefin resin can be used as an encapsulating material for various optoelectronic devices It is possible to provide an encapsulating material which is used for the production of ashes and has improved adhesion with the front substrate and the backsheet contained in the device, particularly long-term adhesive property and heat resistance. Further, The workability and economical efficiency of the device manufacturing can be maintained to be excellent.
Figs. 1 and 2 are graphs of differential scanning calorimetry analysis of polyolefin resins prepared according to Production Examples 1 to 3 of the present application.
FIGS. 3 and 4 are graphs of differential scanning calorimetry analysis of the polyolefin resin prepared according to Comparative Preparation Example 1 of the present application. FIG.
5 is a graph showing UV / Vis spectroscopy according to Experimental Example 2 of the samples prepared in Examples 3 and 8 of the present application.
6 is a graph showing UV / Vis spectroscopy according to Experimental Example 2 of the samples prepared in Comparative Examples 1 and 2 of the present application.
7 and 8 are cross-sectional views exemplarily showing a solar cell module which is an optoelectronic device according to one example of the present application.
Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited by the following examples.
The physical properties in the following examples and comparative examples were evaluated in the following manner.
1. Crystallization temperature ( Tc )
The polymers obtained in Preparative Examples 1 to 3 and Comparative Preparative Example 1 were heated at a rate of 10 占 폚 / min from a temperature of 200 占 폚 to -150 占 폚 while being cooled at a rate of a heat of flow measured by a differential scanning calorimetry (DSC) The crystallization temperature (Tc) was confirmed through peak analysis of the cooling curve. The DSC analysis results of Production Examples 1 to 3 and the DSC analysis result of Comparative Production Example 1 are shown in FIG. 1 and FIG. 3, respectively.
2. Melting temperature ( Tm )
With respect to the polymers obtained in the following Production Examples 1 to 3 and Comparative Production Example 1, the crystallization temperature was measured while cooling the sample at a rate of 10 ° C / min from the temperature of 200 ° C to -150 ° C, The melting temperature (Tm) was confirmed through a peak analysis of the heating curve of the heat flow measured by DSC while raising the temperature to 200 ° C at a rate of 10 ° C / min. The DSC analysis results of Production Examples 1 to 3 Fig. 2 shows the results of DSC analysis of Comparative Production Example 1, and Fig.
3. Measurement of Melt Index
The weights of samples flowing at a weight of 2.16 kg at a temperature of 190 ° C under the conditions of ASTM D-1238-04 under the following Production Examples 1 to 3 and Comparative Production Example 1 were measured to determine the melt index Respectively.
≪ Preparation of ethylene / alpha -olefin copolymer &
Manufacturing example One
A hexane solvent (1.0 L) and 6.4 mmol of 1-octene were added to a 2 L autoclave reactor, and then the temperature of the reactor was preheated to 120 ° C. A 25 mL catalyst storage tank was charged with a compound (0.5 μmol) of the following formula (9), treated with triisobutylaluminum compound (10 μmol), and a dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst (10 μmol) Al: Ti molar ratio 10). Ethylene pressure (35 bar) was then charged into the autoclave reactor, and the catalyst composition was injected into the reactor using argon gas at a high pressure to conduct the copolymerization reaction for 10 minutes. Next, the remaining ethylene gas was removed and the polymer solution was added to excess ethanol to induce precipitation. The precipitated polymer was washed with ethanol and acetone two to three times, respectively, and then dried in a vacuum oven at 80 캜 for 12 hours or more to obtain ethylene-1-octene having a density of 0.862 g / ml.
[Chemical Formula 9]
The crystallization temperature (Tc) and the melting temperature (Tm) of the ethylene-1-octene resin obtained in Production Example 1 were measured using DSC.
Manufacturing example 2
Was prepared in the same manner as in Production Example 1 to obtain ethylene-1-octene having a density of 0.859 g / ml.
The crystallization temperature (Tc) and the melting temperature (Tm) of the ethylene-1-octene resin obtained in Production Example 2 were measured using DSC, and the results are shown in Table 1.
Manufacturing example 3
Was prepared in the same manner as in Production Example 1 to obtain ethylene-1-octene having a density of 0.869 g / ml.
The crystallization temperature (Tc) and the melting temperature (Tm) of the ethylene-1-octene resin obtained in Production Example 3 were measured by DSC, and the results are shown in Table 1.
compare Manufacturing example One
An ethylene-1-octene polymer having a density of 0.866 g / ml was obtained in the same manner as in Production Example 1 except that 0.5 μmol of the compound of the following formula (10) was added instead of the dinuclear catalyst used in Production Example 1.
[Chemical formula 10]
The crystallization temperature (Tc) and the melting temperature (Tm) of the ethylene-1-octene resin obtained in Comparative Preparation Example 1 were measured using DSC.
(° C)
(° C)
<Preparation of Modified Ethylene /? - olefin Copolymer>
Manufacturing example 4
95.01 parts by weight of an ethylene /? - olefin copolymer having a density of 0.862 g / cm 3 and a MFR of 1.12 g / 10 min under a load of 2.16 kg as prepared in Preparation Example 1, 95.01 parts by weight of vinyltrimethoxysilane ), 4.79 parts by weight, 0.1 part by weight of 3-aminopropyltrimethoxysilane (APTMS) and 0.1 part by weight of 2,5-bis (t-butylperoxy) -2,5-dimethylhexane 0.1 part by weight of tert-butylperoxy) -2,5-dimethylhexane (Luperox®101) was graft-extruded (heated, melted and stirred) at 220 ° C. using a twin-screw extruder to obtain a master batch of the modified ethylene / . (Based on 100 parts by weight of the total, each part by weight represents wt%).
Manufacturing example 5
An ethylene /? - olefin copolymer having a density of 0.859 g / cm 3 and a MFR of 0.68 g / 10 min under a load of 2.16 kg as prepared in Production Example 2 was used instead of the ethylene /? - olefin copolymer prepared in Production Example 1 A master batch of the modified ethylene /? - olefin copolymer was prepared in the same manner as in Production Example 4, except that the copolymer was used.
Manufacturing example 6
An ethylene /? - olefin copolymer having a density of 0.869 g / cm 3 and a MFR of 4.2 g / 10 min under a load of 2.16 kg as prepared in Production Example 3 instead of the ethylene /? - olefin copolymer prepared in Production Example 1 A master batch of the modified ethylene /? - olefin copolymer was prepared in the same manner as in Production Example 4, except that the copolymer was used.
Manufacturing example 7
4.79 parts by weight of vinyltrimethoxysilane used in Production Example 6, 0.1 part by weight of 3-aminopropyltrimethoxysilane and 0.1 part by weight of 2,5-bis (t-butylperoxy) -2,5-dimethylhexane Except that 4.89 parts by weight of vinyltrimethoxysilane and 0.1 part by weight of 2,5-bis (t-butylperoxy) -2,5-dimethylhexane were used in place of the modified ethylene /? - olefin A master batch of the copolymer was prepared.
Manufacturing example 8
Except that 0.1 part by weight of 3-aminopropyltriethoxysilane was used instead of 0.1 part by weight of 3-aminopropyltrimethoxysilane used in Production Example 6 to obtain a modified ethylene /? - olefin copolymer Was prepared.
compare Manufacturing example 2
Α-olefin copolymer having a density of 0.866 g / cm 3 and an MFR of 1.27 g / 10 min at 190 ° C. under a load of 2.16 kg, which was prepared in Comparative Preparation Example 1, instead of the ethylene / α- Olefin copolymer was used in place of the ethylene /? - olefin copolymer prepared in Preparation Example 1 to prepare a master batch of the modified ethylene /? - olefin copolymer.
< Encapsulant And photovoltaic module &
Example One
200 g and 400 g of the master batch of the modified ethylene /? - olefin copolymer prepared in Preparation Example 4 and the ethylene /? - olefin copolymer prepared in Preparation Example 1 were prepared and mixed in a ratio of 1: 2 18 g of an additive masterbatch which contained 3000 ppm of a light stabilizer (Songlight 7700), 1000 ppm of a UV absorber (TINUVIN UV531), 500 ppm of an antioxidant 1 (Irganox 1010) and 500 ppm of an antioxidant 2 (Irgafos 168) And then fed into a hopper of a film forming machine having a twin-screw extruder (φ19 mm) and a T die (width: 200 mm), and processed at an extrusion temperature of 180 ° C. and a take-off speed of 3 m / Sealing material.
(Thickness: about 8 mm), the sealing material having a thickness of 500 mu m prepared above, the crystalline silicon wafer photovoltaic device, the sealing material having the thickness of 500 mu m and the backsheet (polyvinyl fluoride resin sheet having a thickness of 20 mu m, A PVDF / PET / PVDF) laminate of a polyethylene terephthalate film having a thickness of 250 占 퐉 and a polyvinyl fluoride resin sheet having a thickness of 20 占 퐉 was laminated in this order and pressed in a vacuum laminator at 110 占 폚 for 15 minutes and 30 seconds to form a photovoltaic module Respectively.
Example 2
The master batch of the modified ethylene /? - olefin copolymer prepared in Production Example 5 was used in place of the modified ethylene /? - olefin copolymer prepared in Production Example 4, and the ethylene /? - A sheet-like encapsulant and a photovoltaic module were prepared in the same manner as in Example 1, except that the ethylene /? - olefin copolymer prepared in Preparation Example 2 was used instead of the olefin copolymer.
Example 3
The master batch of the modified ethylene /? - olefin copolymer prepared in Production Example 6 was used instead of the modified ethylene /? - olefin copolymer prepared in Production Example 4, and the ethylene /? - Sheet encapsulant and a photovoltaic module were prepared in the same manner as in Example 1, except that the ethylene /? - olefin copolymer prepared in Preparation Example 3 was used instead of the olefin copolymer.
Example 4
Except that the master batch of the modified ethylene /? - olefin copolymer prepared in Production Example 7 was used instead of the modified ethylene /? - olefin copolymer prepared in Production Example 6, Encapsulant and photovoltaic module were fabricated.
Example 5
Except that the master batch of the modified ethylene /? - olefin copolymer prepared in Production Example 8 was used in place of the modified ethylene /? - olefin copolymer prepared in Production Example 6, Encapsulant and photovoltaic module were fabricated.
Example 6 to 10
A photovoltaic module was manufactured in the same manner as in Examples 1 to 5, except that each was pressed in a vacuum laminator at 150 DEG C for 15 minutes and 30 seconds.
Comparative Example One
The master batch of the modified ethylene /? - olefin copolymer prepared in Comparative Preparation Example 2 was used instead of the master batch of the modified ethylene /? - olefin copolymer prepared in Preparation Example 1, and the ethylene / except that the ethylene /? - olefin copolymer prepared in Comparative Preparation Example 1 was used in place of the? -olefin copolymer prepared in Comparative Preparation Example 1, thereby preparing a sheet-like encapsulant and a photovoltaic module.
Comparative Example 2
A photovoltaic module was fabricated in the same manner as in Comparative Example 1, except that it was pressed in a vacuum laminator at 150 캜 for 15 minutes and 30 seconds.
Experimental Example
1. Measurement of 90 degree peel strength
In order to measure the peel strength of the encapsulant prepared in Examples 1 to 3, 5 and 10 and Comparative Example 1, specimens similar to the manufactured photovoltaic module were separately prepared. The test piece was made of a glass plate (thickness: about 8 mm), the sealing material and the backing sheet (thickness: 20 탆, polyethyleneterephthalate having a thickness of 250 탆 and polyvinyl fluoride Laminated sheet of a resin sheet: PVDF / PET / PVDF) were laminated in this order, and lamination temperature was changed in the vacuum laminator according to the conditions shown in Table 2 below for lamination for 15 minutes. After fixing the lower glass plate of the manufactured specimen, the sealing material adhered to the backsheet was peeled off at a stretching speed of 50 mm / min and a peeling angle of 90 degrees at the same time as the 15 mm wide rectangle in accordance with ASTM D1897 The strengths are shown in Table 2 below.
Base resin (content, density)
Lamy temperature (℃)
Peel strength
(N / 15 mm)
(wt%)
(d = 0.862)
0.1
(d = 0.859)
0.1
(d = 0.869)
0.1
(d = 0.869)
0.1
(d = 0.869)
0.1
0.1
* VTMS: vinyltrimethoxysilane
APTMS: 3-aminopropyltrimethoxysilane
* APTES: 3-aminopropyltriethoxysilane
2. Light transmittance And Hayes's Measure
In order to measure the light transmittance and haze of the sealing material in Examples 3 to 5, 8 to 10 and Comparative Examples 1 and 2, separate specimens were separately prepared. The specimens were prepared by stacking two sheets of the sealing material having a thickness of 500 탆 produced in the above manner between two glass plates (thickness: about 1 mm) and laminating the laminate with different lamination temperatures in the vacuum laminator as shown in Table 3, Was used to make the sum of the thicknesses of the two sheets of overlapping encapsulant sheets constant to about 500 ± 50 μm and the total light transmittance and haze value of the light with a wavelength of 550 nm was measured using a hazemeter, Table 3 shows the results. In this case, the transmittance and the haze value were measured by placing the specimen in the specimen holder three times, and then the average value of the transmittance and the haze value was measured under the standard conditions of JIS K 7105. In addition, the total light transmittance of light with a wavelength of 200 to 1300 nm was measured using UV / Vis spectroscopy and is shown in FIGS. 5 to 6 below. The lamination process time was fixed at 5 min vacuum / 30 sec press / 10 min retain pressure.
< UV / Vis Spectrocopy Equipment measurement conditions>
Slit width: 32 nm
Detector unit: External (2D detectors)
Time constant: 0.2 sec
As can be seen in Table 3 and FIG. 5, the samples laminated at a low temperature of 110 DEG C exhibit low haze and high total light transmittance.
That is, through Examples 1 to 8 and Comparative Examples 1 to 2 and experimental examples thereof, the encapsulant for an optoelectronic device manufactured by using the resin composition comprising a polyolefin resin having two crystallization temperatures has a low temperature And exhibits a high total light transmittance and a low haze value, it is possible to perform lamination at a lower temperature in the conventional process, and it is confirmed that the light transmittance and production efficiency of the encapsulating material sheet can be improved .
1, 2: Solar cell module
11, 21: front substrate
12, 22: back sheet
13, 23: photovoltaic device
14 (a), 14 (b), 24: Encapsulation material
Claims (13)
[Formula 1]
10 ° C ≤ | Tc 2 -Tc 1 | - | Tm-Tc 2 | ≤ 20 ° C
In the general formula 1,
Tc 1 represents a first crystallization temperature,
Tc < 2 > represents a second crystallization temperature,
Tm represents the melting temperature.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/KR2014/010307 WO2015065069A1 (en) | 2013-10-30 | 2014-10-30 | Olefin resin |
| JP2016527207A JP6355733B2 (en) | 2013-10-30 | 2014-10-30 | Olefin resin |
| US15/033,233 US9605099B2 (en) | 2013-10-30 | 2014-10-30 | Olefin resin |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020130130503 | 2013-10-30 | ||
| KR20130130503 | 2013-10-30 |
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| KR101618980B1 true KR101618980B1 (en) | 2016-05-09 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001002863A (en) | 1999-04-20 | 2001-01-09 | Japan Polychem Corp | Thermoplastic resin composition |
| JP2011089140A (en) | 2011-02-09 | 2011-05-06 | Sumitomo Chemical Co Ltd | Olefinic resin composition for foam-molding and foam |
| KR101097378B1 (en) | 2010-07-01 | 2011-12-23 | 주식회사 엘지화학 | Olefin-based polymer and method for producing the same |
| US20130137833A1 (en) | 2010-06-25 | 2013-05-30 | Japan Polyethylene Corporation | Resin composition for solar cell encapsulant, and solar cell encapsulant and solar cell module using the same |
-
2014
- 2014-10-30 KR KR1020140149266A patent/KR101618980B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001002863A (en) | 1999-04-20 | 2001-01-09 | Japan Polychem Corp | Thermoplastic resin composition |
| US20130137833A1 (en) | 2010-06-25 | 2013-05-30 | Japan Polyethylene Corporation | Resin composition for solar cell encapsulant, and solar cell encapsulant and solar cell module using the same |
| KR101097378B1 (en) | 2010-07-01 | 2011-12-23 | 주식회사 엘지화학 | Olefin-based polymer and method for producing the same |
| JP2011089140A (en) | 2011-02-09 | 2011-05-06 | Sumitomo Chemical Co Ltd | Olefinic resin composition for foam-molding and foam |
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