Laminated molded article

A technology of laminated molding and molded products, which is applied in the direction of coating, layered products, metal layered products, etc., can solve the problem of no disclosure of the adhesion between the metal vapor deposition layer and the resin composition, and achieve excellent adhesion , the effect of high surface reflectivity

Active Publication Date: 2018-04-17

ASAHI KASEI KOGYO KK

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AI-Extracted Technical Summary

Problems solved by technology

[0007] In addition, in order to improve the appearance of the metal surface of a laminated molded article, a technique of using an olefin resin in a resin composition ...

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Method used

In polyphenylene ether (i), it is preferable to contain the structural unit represented by the above chemical formula (3) in the range of 0.01 to 10 per 100 monomer units constituting polyphenylene ether, more preferably 0.01 The range of 1 to 5 contains the structural unit represented by said chemical formula (3). By setting the structural unit represented by the chemical formula (3) to 0.01 to 10, a good surface reflectance can be maintained even in a laminated molded article exposed to high temperature and high humidity conditions for a long time, and this range is particularly more preferable. 5 or less.

In the existing polyphenylene ether, when exposed to high temperature for a long time, the methyl group located in the terminal unit (hereinafter also referred to as "terminal methyl group"), the methyl group located in the middle unit (hereinafter also referred to as "terminal methyl group"), Oxidative crosslinking reaction may occur at the hydroxyl group located in the terminal unit (in this specification, also referred to as "terminal hydroxyl group"). The inventors of the present invention focused on the oxidative crosslinking reaction of the terminal methyl group or the side chain methyl group, etc., and studied the possibility of suppressing the oxidative crosslinking reaction to further suppress the formation of the metal thin film layer on the surface of the molded article. Depression, the possibility of further suppressing the deterioration of the mirror surface appearance of the metal thin film layer due to the development of the depression. It is understood that terminal methyl groups, side chain methyl groups, and terminal hydroxyl groups tend to generate free radicals more easily, and the generated free radicals may be the main cause of oxidative crosslinking. It is presumed that in the polyphenylene ether (i) containing one or more structural units selected from the above chemical formulas (1), (2) and (3), the oxidized site (terminal methyl group, side chain methyl group) group, terminal hydroxyl group) is capped in a state substituted by a specific molecule, and the cr...

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Abstract

The invention provides a laminated molded article having high surface reflectance and excellent close adhesion between a molded product formed from a resin composition and a metal thin-film layer. Thelaminated molded article includes a molded product formed from a resin composition and a metal thin-film layer. The resin composition contains a polyphenylene ether resin (A) and an amorphous [alpha]-olefin copolymer (B). The polyphenylene ether resin (A) includes a polyphenylene ether (i) and a compound (ii) being at least one compound selected from the group consisting of: an organophosphorus compound having, in molecules thereof, a chemical structure represented by formula (I) or (II), where R in formula (II) is a trivalent saturated hydrocarbon group having a carbon number of 1 to 8 or atrivalent aromatic hydrocarbon group having a carbon number of 6 to 12; and a phosphonic acid, phosphonic acid ester, phosphinic acid, phosphinic acid ester, monocarboxylic acid, sulfonic acid, sulfinic acid, or carbonate other than the organophosphorus compound in amounts of 95 mass % to 99.95 mass % of the component (i) and 0.05 mass % to 5 mass % of the component (ii) relative to 100 mass %, intotal, of the components (i) and (ii).

Application Domain

Vacuum evaporation coatingSputtering coating +2

Technology Topic

Phosphinic AcidsEther +12

Image

Examples

Experimental program(7)
Comparison scheme(2)

Example Embodiment

[0283] [Examples 1, 8, 14, 15]

[0284] (I-1) 70 parts by mass and (ii) 0.7 parts by mass were mixed with a drum mixer, and the powder mixture was mixed from a TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., cylinder number 13, screw diameter 58mm, L/D=53; It is supplied at the most upstream part (the top feed port) of the screw mode with kneading disk L: 2, kneading disk R: 14 and kneading disk N: 2 at the barrel temperature Melt-kneading was performed under conditions of 300°C, a screw rotation speed of 400 rpm, an extrusion speed of 400 kg/hr, and a vent vacuum degree of 7.998 kPa (60 Torr) to obtain pellets. After dissolving the pellets in chloroform, they were reprecipitated with methanol to extract the polyphenylene ether component. Then, it vacuum-dried at 60 degreeC for 4 hours, and obtained the powder of polyphenylene ether.

[0285] The obtained polyphenylene ether powder can be used 31 P-NMR (single plus method) and 1 H-NMR was used for identification, and the addition amount of the reactive compound was determined by 1 It is obtained by dividing the integrated value of the peak appearing at 2.8 ppm to 3.6 ppm in H-NMR by the integrated value of the peak at 6.0 ppm to 7.0 ppm derived from the aromatic ring of polyphenylene ether. It is confirmed that every 100 units in the polyphenylene ether chain In the monomers, the structural units of the following chemical formulas (9) and (10) contain 0.30 in total.

[0286] 【化26】

[0287]

[0288] 【化27】

[0289]

[0290] 31 P-NMR measurement conditions

[0291] Device: JEOL RESONANCE ECS400

[0292] Observation core: 31 P

[0293] Observation frequency: 161.8MHz

[0294] Pulse width: 45°

[0295] Waiting time: 5 seconds

[0296] Points: 10,000 times

[0297] Solvent: CDCl 3

[0298] Sample concentration: 20w/v%

[0299] Chemical shift standard: 85% phosphoric acid aqueous solution (external standard) 0ppm

[0300] 1 H-NMR measurement conditions

[0301] Device: JEOL-ECA500

[0302] Observation core: 1 H

[0303] Observation frequency: 500.16MHz

[0304] Measurement method: Single-Plus

[0305] Pulse width: 7μsec

[0306] Waiting time: 5 seconds

[0307] Points: 512 times

[0308] Solvent: CDCl 3

[0309] Sample concentration: 5w%

[0310] Chemical shift standard: TMS 0.00ppm

[0311] In the following, polyphenylene ether 31 P-NMR and 1 The H-NMR measurement was performed under the above conditions.

[0312] Furthermore, the amount of addition on the terminal hydroxyl group can be used 13 C-NMR, using 146.4ppm (the carbon adjacent to the oxygen atom of the ether bond (which is formed by adding a reactive compound to the OH group)) peak integral value [A], 145.4ppm (with the OH group) The integral value [B] of adjacent carbon) was calculated by the following mathematical formula (1), and it was confirmed that 0.02 structural units of the following chemical formula (11) were included in every 100 monomer units constituting the polyphenylene ether.

[0313] The number of additions of reactive compounds per 100 monomer units constituting the polyphenylene ether (units) = (the number of terminal OHs per 100 monomer units constituting the precursor polyphenylene ether)×{[A] /([A]+[B])}···(1)

[0314] In addition, use 1 H-NMR confirmed that no new doublet was produced at 3.5 ppm to 5.5 ppm.

[0315] 【化28】

[0316]

[0317] 13 C-NMR measurement conditions

[0318] Device: Bruker Biospin Avance 600

[0319] Observation core: 13 C

[0320] Observation frequency: 150.9MHz

[0321] Measurement method: anti-gating decoupling method

[0322] Pulse width: 30°

[0323] Waiting time: 10 seconds

[0324] Points: 2,000 times

[0325] Solvent: CDCl 3

[0326] Sample concentration: 20w/v%

[0327] Chemical shift standard: TMS 0ppm

[0328] In the following, polyphenylene ether 13 The C-NMR measurement was performed under the above conditions.

[0329] The ratio of the structural unit of chemical formula (9) to the structural unit of chemical formula (10) is determined by using 31 P-NMR calculated the ratio of the peak integral value of 34 ppm to 36 ppm derived from the structural unit of chemical formula (9) to the peak integral value of 38 ppm to 42 ppm derived from the structural unit of chemical formula (10), and it was 25 Mol%.

[0330] Using the obtained pellets, styrene resin (GPPS), elastomer component (SEBS), antioxidant (PEP-36), and amorphous α-olefin copolymer (B-1), as shown in Tables 1 and 2 The mixing ratio shown is from a TEM58SS twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., barrel number 13, screw diameter 58mm, L/D=53); with kneading disc L: 2 and kneading disc R: 14 And the most upstream part (top feed port) of kneading disc N: 2 screw mode), the cylinder temperature is 300℃, the screw speed is 400rpm, the extrusion speed is 400kg/hr, and the vacuum degree of the exhaust port The melt-kneading was performed under the conditions of 7.998 kPa (60 Torr) to obtain a resin composition.

Example Embodiment

[0331] [Example 2, 10]

[0332] A mixture of (i-2) 70 parts by mass and (ii) 0.7 parts by mass was melt-kneaded in the same manner as in Example 1 to obtain pellets. The obtained pellets were made into polyphenylene ether powder, and the addition amount of the reactive compound was quantified in the same manner as in Example 1. As a result, it was confirmed that the chemical formula (9) per 100 monomer units in the polyphenylene ether chain The structural unit of (10) contains 0.26 in total.

[0333] Furthermore, the amount of addition on the terminal hydroxyl group can be used 13 C-NMR, using 146.4ppm (the carbon adjacent to the oxygen atom of the ether bond (which is formed by adding a reactive compound to the OH group)) peak integral value [A], 145.4ppm (with the OH group) The integral value [B] of the adjacent carbon) was obtained by the above-mentioned mathematical formula (1), and it was confirmed that every 100 monomer units constituting the polyphenylene ether contained 0.04 structural units of the chemical formula (11). In addition, use 1 H-NMR confirmed that no new double peaks were generated at 3.5 ppm to 5.5 ppm.

[0334] The ratio of the structural unit of chemical formula (9) to the structural unit of chemical formula (10) is determined by using 31 P-NMR calculated the ratio of the peak integral value of 34 ppm to 36 ppm derived from the structural unit of chemical formula (9) to the peak integral value of 38 ppm to 42 ppm derived from the structural unit of chemical formula (10), and it was 27 Mol%.

[0335] Using the obtained pellets, styrene resin (GPPS), elastomer component (SEBS), antioxidant (PEP-36), and amorphous α-olefin copolymer (B-1), as shown in Table 1 The mixing ratio is melt-kneaded to obtain a resin composition.

Example Embodiment

[0336] [Examples 3, 4, 5, 6, 7, 12, 18]

[0337] A mixture of (i-1) 40 parts by mass, (i-2) 30 parts by mass, and (ii) 0.7 parts by mass was melt-kneaded in the same manner as in Example 1 to obtain pellets. The obtained pellets were made into polyphenylene ether powder, and the addition amount of the reactive compound was quantified in the same manner as in Example 1. As a result, it was confirmed that the chemical formula (9) per 100 monomer units in the polyphenylene ether chain , The structural unit of (10) contains 0.28 in total.

[0338] Furthermore, the amount of addition on the terminal hydroxyl group can be used 13 C-NMR, using 146.4ppm (the carbon adjacent to the oxygen atom of the ether bond (which is formed by adding a reactive compound to the OH group)) peak integral value [A], 145.4ppm (with the OH group) The integral value [B] of the adjacent carbon) was obtained by the above-mentioned mathematical formula (1), and it was confirmed that every 100 monomer units constituting the polyphenylene ether contained 0.03 structural units of the chemical formula (11). In addition, use 1 H-NMR confirmed that no new double peaks were generated at 3.5 ppm to 5.5 ppm.

[0339] The ratio of the structural unit of chemical formula (9) to the structural unit of chemical formula (10) is determined by using 31 P-NMR calculated the ratio of the peak integral value of 34 ppm to 36 ppm derived from the structural unit of chemical formula (9) to the peak integral value of 38 ppm to 42 ppm derived from the structural unit of chemical formula (10), and was calculated as 26 Mol%.

[0340] Using the obtained pellets, styrene resin (GPPS), elastomer component (SEBS), and amorphous α-olefin copolymer (B-1) to (B-3), as shown in Tables 1 and 2 The mixing ratio is melt-kneaded to obtain a resin composition.

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the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine

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