JP2016037542A - Substrate for printed matter protective film - Google Patents
Substrate for printed matter protective film Download PDFInfo
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- JP2016037542A JP2016037542A JP2014161143A JP2014161143A JP2016037542A JP 2016037542 A JP2016037542 A JP 2016037542A JP 2014161143 A JP2014161143 A JP 2014161143A JP 2014161143 A JP2014161143 A JP 2014161143A JP 2016037542 A JP2016037542 A JP 2016037542A
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- printed matter
- substrate
- film
- vinyl chloride
- protective film
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- 230000001681 protective effect Effects 0.000 title claims abstract description 28
- 239000000758 substrate Substances 0.000 title claims abstract description 19
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 239000012965 benzophenone Substances 0.000 claims abstract description 8
- 238000002834 transmittance Methods 0.000 claims abstract description 8
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 6
- 239000003549 soybean oil Substances 0.000 claims abstract description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 30
- 239000004611 light stabiliser Substances 0.000 claims description 12
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- -1 benzophenone compound Chemical class 0.000 abstract description 5
- 238000002845 discoloration Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000000465 moulding Methods 0.000 description 11
- 238000004383 yellowing Methods 0.000 description 10
- 238000005562 fading Methods 0.000 description 6
- 239000012760 heat stabilizer Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000008366 benzophenones Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 2
- DCBNMBIOGUANTC-UHFFFAOYSA-N [5-[(5-benzoyl-4-hydroxy-2-methoxyphenyl)methyl]-2-hydroxy-4-methoxyphenyl]-phenylmethanone Chemical compound COC1=CC(O)=C(C(=O)C=2C=CC=CC=2)C=C1CC(C(=CC=1O)OC)=CC=1C(=O)C1=CC=CC=C1 DCBNMBIOGUANTC-UHFFFAOYSA-N 0.000 description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 description 2
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 125000005590 trimellitic acid group Chemical class 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、写真や紙類などの印刷物の上に貼り付けて、該印刷物を保護するために使用される印刷物保護フィルムの基材に関し、特に、印刷物の退色を防止し、かつ印刷物保護フィルム自体の変色もない印刷物保護フィルム用基材に関する。 The present invention relates to a base material for a printed matter protective film used for protecting a printed matter by sticking it on a printed matter such as a photograph or paper, and in particular, prevents the printed matter from fading and the printed matter protective film itself. It is related with the base material for printed matter protective films which are not discolored.
印刷物の上に印刷物保護フィルムを貼り合わせることは、一般的にラミネート加工と称される。ラミネート加工を施すと、印刷面に艶や耐水性、高級感などを付与することができる。また、特殊な表面形状を有する保護フィルムを用いれば、マット感やシボ感を印刷面に付与することもできる。
このような印刷物保護フィルムは、基材と粘着層、場合によっては、表面層や意匠層を有してなり、印刷物の退色を防止するために、これら基材や粘着層などに、耐候性を高める光安定剤や紫外線吸収剤などが添加されることが多い。
Laminating a printed material protective film on a printed material is generally referred to as laminating. Lamination can give gloss, water resistance, luxury, etc. to the printed surface. Moreover, if the protective film which has a special surface shape is used, a mat feeling and a wrinkle feeling can also be provided to a printing surface.
Such a printed matter protective film has a base material and an adhesive layer, and in some cases, a surface layer and a design layer, and in order to prevent fading of the printed matter, the base material and the adhesive layer have weather resistance. Increasing light stabilizers and UV absorbers are often added.
ポリオレフィン系樹脂製の基材は、添加剤の保持能力が低く、光安定剤や紫外線吸収剤などの添加量が多くなりやすいので、製品品質の低下やコスト的な問題があった。そのうえ、ポリオレフィン系樹脂は、硬度を自由に変えることができないので、局面追従性を必要とする用途には不向きである。
これに対し、特許文献１に記載するような塩化ビニル系樹脂製の基材であれば、無色透明で、硬度も自由に変えることができ、しかも、色々な機能をポリオレフィン系樹脂に比べ少ない添加量によって発揮させやすい。
The base material made of polyolefin resin has a low ability to retain additives, and the amount of light stabilizers and ultraviolet absorbers to be added tends to increase, resulting in product quality degradation and cost problems. Moreover, since the polyolefin resin cannot change the hardness freely, it is not suitable for applications that require a phase following ability.
On the other hand, if it is a base material made of a vinyl chloride resin as described in Patent Document 1, it is colorless and transparent, its hardness can be freely changed, and various functions are added in comparison with polyolefin resins. Easy to show depending on the amount.
ところが、無色透明の塩化ビニル系樹脂に光安定剤や紫外線吸収剤を添加すると、基材（フィルム）の製膜（加熱成形）中ないし製膜後に、フィルム自体の色相が黄色味を帯びてしまう問題があった。 However, when a light stabilizer or UV absorber is added to a colorless and transparent vinyl chloride resin, the hue of the film itself becomes yellowish during or after film formation (heat molding) of the substrate (film). There was a problem.
一方、耐候性の向上を目的として、ブタンテトラカルボン酸を有するヒンダードアミンを配合した塩化ビニル系樹脂製の成形品が提案されている（特許文献２参照）。
しかし、特許文献２の成形品の用途は、雨樋や窓枠などの建材や自動車の内部部品であって、透明性については検討していないうえ、加熱成形中ないし成形直後に起こる（すなわち、光に晒される前に生じてしまう）成形品自体の黄変を防止できるものではなかった。
On the other hand, for the purpose of improving weather resistance, a molded product made of vinyl chloride resin containing a hindered amine having butanetetracarboxylic acid has been proposed (see Patent Document 2).
However, the uses of the molded article of Patent Document 2 are building materials such as rain gutters and window frames, and internal parts of automobiles, and are not examined for transparency, and occur during heating molding or immediately after molding (that is, It was not possible to prevent yellowing of the molded product itself (which occurs before exposure to light).
本発明は、以上の諸点を考慮し、透明性に優れ、印刷物の退色などの経時劣化を防ぐことができ、しかも、塩化ビニル系樹脂製でありながらフィルム自体の変色（特に黄変）をも防止できる、印刷物を保護するためのフィルム用基材を提供することを課題とする。 In consideration of the above points, the present invention is excellent in transparency, can prevent deterioration over time such as fading of printed matter, and also has a color change (particularly yellowing) of the film itself while being made of a vinyl chloride resin. It is an object of the present invention to provide a film base material for protecting printed matter that can be prevented.
本発明者らは、上記の課題を解決するために検討を重ねた結果、塩化ビニル系樹脂が、配合される添加剤やフィルムの製膜（加熱成形）時の環境などによって黄変しやすくなることに着目し、
無限に存在する光安定剤や紫外線吸収剤の中から、ブタンテトラカルボン酸を有するヒンダードアミンとベンゾフェノン系化合物とを選定し、これらを共に塩化ビニル系樹脂中に配合すれば、それぞれの耐候性能を相殺することなく、むしろ経時での色相変化をより確実に抑えることができ、しかも、製膜（加熱成形）中ないし製膜直後に起こる（すなわち、光に晒される前に生じてしまう）フィルム自体の黄変を引き起こさないことを見出した。
As a result of repeated studies to solve the above problems, the inventors of the present invention are prone to yellowing the vinyl chloride resin depending on the additive to be blended and the environment during film formation (heat molding). Focus on
By selecting hindered amines with butanetetracarboxylic acid and benzophenone compounds from infinitely existing light stabilizers and UV absorbers, and blending them together in vinyl chloride resin, each weather resistance performance is offset. Rather, the change in hue over time can be more reliably suppressed, and the film itself that occurs during film formation (heat forming) or immediately after film formation (that is, occurs before being exposed to light) Found no yellowing.
本発明は、このような知見の下でなし得たものであり、以下を要旨とする。
（１） 印刷物を保護するためのフィルム用基材であって、
塩化ビニル系樹脂１００重量部に対し、１０〜３０重量部の可塑剤と、
光安定剤として、ブタンテトラカルボン酸を有するヒンダードアミン、
紫外線吸収剤として、ベンゾフェノン系化合物
とを含んでなり、かつＪＩＳ Ｋ７１０５に準じて測定される全光線透過率が８０％以上であることを特徴とする印刷物保護フィルム用基材。
（２） さらに、エポキシ化大豆油とバリウム−亜鉛系化合物を含むことを特徴とする前記（１）に記載の印刷物保護フィルム用基材。
（３） サンシャインウェザーメーターにより、ブラックパネル温度６３℃、６０分当たり１２分の水噴射の条件下、２０００時間経過した後の色相変化ΔＥ値が１．０以下であることを特徴とする前記（１）または（２）に記載の印刷物保護フィルム用基材。
The present invention has been achieved under such knowledge, and the gist thereof is as follows.
(1) A film substrate for protecting printed matter,
10 to 30 parts by weight of a plasticizer with respect to 100 parts by weight of the vinyl chloride resin;
As a light stabilizer, a hindered amine having butanetetracarboxylic acid,
A substrate for a printed matter protective film comprising a benzophenone-based compound as an ultraviolet absorber and having a total light transmittance of 80% or more measured according to JIS K7105.
(2) The printed material protective film substrate according to (1), further comprising epoxidized soybean oil and a barium-zinc compound.
(3) The hue change ΔE value after 2000 hours is 1.0 or less under the conditions of a black panel temperature of 63 ° C. and water injection of 12 minutes per 60 minutes by a sunshine weather meter, The base material for printed matter protective films as described in 1) or (2).
本発明の印刷物保護フィルム用基材は、成形性（製膜性）や透明性に優れるうえ、製膜（加熱成形）中ないし製膜直後に懸念される基材自体の黄変を引き起こさない。また、本発明の基材を用いた保護フィルムにてラミネート加工された印刷物は、経時使用に伴う色やけ、退色などの色相変化が生じにくいので、耐候性に非常に優れたものである。
このため、長期に亘って紫外線などの光に晒される印刷物を保護するフィルムの基材用途として最適である。
The substrate for printed matter protective film of the present invention is excellent in moldability (film forming property) and transparency, and does not cause yellowing of the substrate itself which is a concern during film formation (heat forming) or immediately after film formation. In addition, the printed matter laminated with the protective film using the base material of the present invention is very excellent in weather resistance because the hue change such as discoloration, fading and fading with use over time hardly occurs.
For this reason, it is optimal as a base material application of a film that protects printed matter exposed to light such as ultraviolet rays over a long period of time.
本発明は、印刷物を保護するためのフィルム用の基材であって、塩化ビニル系樹脂１００重量部に対し、１０〜３０重量部の可塑剤を含む。
１０重量部未満だと、製膜（成形）が困難になり、良好な基材が得られにくく、３０重量部を超えると、コシがなくなり、印刷物保護フィルムに用いる基材としては不適であり、好ましくは１５〜２５重量部である。
The present invention is a film substrate for protecting printed matter, and contains 10 to 30 parts by weight of a plasticizer with respect to 100 parts by weight of a vinyl chloride resin.
If it is less than 10 parts by weight, film formation (molding) becomes difficult, and it is difficult to obtain a good base material. If it exceeds 30 parts by weight, there is no stiffness and it is unsuitable as a base material used for a printed matter protective film, Preferably it is 15-25 weight part.
可塑剤としては、通常の塩化ビニル系樹脂に使用されている化合物が使用でき、具体的にはフタル酸ジオクチル（ＤＯＰ）、ジイソノニルフタレート(ＤＩＮＰ)、ジイソデシルフタレート(ＤＩＤＰ)、ジブチルフタレート(ＤＢＰ)、ジウンデシルフタレート(ＤＵＰ)、ブチルベンジルフタレート(ＢＢＰ)などに代表されるフタル酸エステル系、トリオクチルトリメリテート(ＴＯＴＭ)などに代表されるトリメリット酸エステル系、ジオクチルアジペート(ＤＯＡ)、ジオクチルセバケート(ＤＯＳ)、ジオクチルアゼレート(ＤＯＺ)などに代表される脂肪酸エステル系、ポリプロピレンアジペートなどに代表されるポリエステル系などの可塑剤を使用することができる。 As the plasticizer, compounds used in ordinary vinyl chloride resins can be used. Specifically, dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), dibutyl phthalate (DBP), Phthalic acid esters such as diundecyl phthalate (DUP) and butyl benzyl phthalate (BBP), trimellitic acid esters such as trioctyl trimellitate (TOTM), dioctyl adipate (DOA), dioctyl seba Plasticizers such as fatty acid ester type typified by Kate (DOS) and dioctyl azelate (DOZ), polyester type typified by polypropylene adipate and the like can be used.
本発明では、上記可塑剤の助剤として、エポキシ化大豆油を添加することもできる。エポキシ化大豆油の添加量は、製膜性の向上なども考慮すると、塩化ビニル系樹脂１００重量部に対し、１〜１０重量部程度とすればよい。
エポキシ化大豆油は、後述のバリウム−亜鉛系熱安定剤との併用により、製膜時などの熱による塩化ビニル系樹脂の黄変現象をより一層防止することができる。
In the present invention, epoxidized soybean oil can be added as an auxiliary to the plasticizer. The addition amount of the epoxidized soybean oil may be about 1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin considering the improvement of film forming property.
Epoxidized soybean oil can further prevent the yellowing phenomenon of the vinyl chloride resin due to heat during film formation, etc., in combination with a barium-zinc heat stabilizer described later.
塩化ビニル系樹脂としては、塩化ビニルモノマーの単独重合体、塩化ビニルモノマーと、酢酸ビニルモノマー、アクリロニトリルモノマーなどの塩化ビニルモノマーと共重合可能なモノマーとの共重合体、及びこれら重合体の後塩素化物を使用することができる。
上記塩化ビニル系樹脂の平均重合度は、小さすぎると、得られる保護フィルムの耐傷性に劣り、大きすぎれば、厚さ３００μｍ以下のフィルムに成形する際の製膜性が低下するので、８００〜１４００程度が好ましい。
Examples of the vinyl chloride resin include vinyl chloride monomer homopolymers, copolymers of vinyl chloride monomers and monomers copolymerizable with vinyl chloride monomers such as vinyl acetate monomers and acrylonitrile monomers, and post-chlorine of these polymers. Compounds can be used.
If the average degree of polymerization of the vinyl chloride resin is too small, the resulting protective film is inferior in scratch resistance, and if it is too large, the film-forming property at the time of molding into a film having a thickness of 300 μm or less is lowered. About 1400 is preferable.
本発明の印刷物保護フィルム用基材は、光安定剤として、ブタンテトラカルボン酸を有するヒンダードアミンを含む。ブタンテトラカルボン酸を有さないヒンダードアミン系の光安定剤では、印刷物保護フィルム用の基材として要求される十分な耐候性が得られないことがある。
ブタンテトラカルボン酸を有するヒンダードアミンとしては、例えば、下記の一般式（Ｉ）で表される化合物や、一般式（ＩＩ）で表される化合物などが挙げられるが、これらは単独で用いても、２種以上を混合して用いてもよい。
The base material for printed matter protective films of the present invention contains a hindered amine having butanetetracarboxylic acid as a light stabilizer. A hindered amine light stabilizer that does not have butanetetracarboxylic acid may not provide sufficient weather resistance required as a substrate for a printed matter protective film.
Examples of the hindered amine having butanetetracarboxylic acid include a compound represented by the following general formula (I), a compound represented by the general formula (II), and the like. Two or more kinds may be mixed and used.
上記のようなブタンテトラカルボン酸を有するヒンダードアミンの中でも、分子量が小さい化合物ではブリードアウトしやすい傾向があるので、分子量が１５００以上の化合物が好ましく、さらに好ましくは一般式（ＩＩ）に示す化合物である。
また、ブタンテトラカルボン酸を有するヒンダードアミンの添加量は、塩化ビニル系樹脂１００重量部に対し、０．０１〜０．５重量部程度が好ましく、より好ましくは０．１〜０．３重量部である。
Among the hindered amines having a butanetetracarboxylic acid as described above, compounds having a low molecular weight tend to bleed out, so a compound having a molecular weight of 1500 or more is preferable, and a compound represented by the general formula (II) is more preferable. .
The amount of hindered amine having butanetetracarboxylic acid is preferably about 0.01 to 0.5 parts by weight, more preferably 0.1 to 0.3 parts by weight, relative to 100 parts by weight of the vinyl chloride resin. is there.
本発明の印刷物保護フィルム用基材は、紫外線吸収剤として、ベンゾフェノン系化合物を含む。例えば、ベンゾトリアゾール系の紫外線吸収剤では、製膜時や製膜後に黄変が見られたり、十分な耐候性が得られないことがある。
ベンゾフェノン系化合物としては、例えば、２，４−ジーヒドロキシベンゾフェノン、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２，２'−ジヒドロキシ−４，４'−ジメトキシベンゾフェノン、ビス（５−ベンゾイル−４−ヒドロキシ−２−メトキシフェニル）メタン、１，４−ビス（４−ベンゾイル−３−ヒドロキシフェノン）−ブタン等が挙げられるが、これらは単独でまたは２種以上組み合わせて使用することもできる。
上記ベンゾフェノン系化合物の中でも、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン、ビス（５−ベンゾイル−４−ヒドロキシ−２−メトキシフェニル）メタン等の分子量が３００以上の化合物であると紫外線の捕捉容量が大きいため好ましい。
また、ベンゾフェノン系化合物の添加量は、塩化ビニル系樹脂１００重量部に対し、０．０５〜１．５重量部程度が好ましく、より好ましくは０．５〜１．０重量部である。
The base material for printed matter protective films of the present invention contains a benzophenone-based compound as an ultraviolet absorber. For example, with a benzotriazole-based ultraviolet absorber, yellowing may be observed during film formation or after film formation, or sufficient weather resistance may not be obtained.
Examples of the benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy. Examples thereof include benzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 1,4-bis (4-benzoyl-3-hydroxyphenone) -butane, and these are used alone or in combination of two or more. It can also be used in combination.
Among the above-mentioned benzophenone compounds, ultraviolet ray trapping capacity is a compound having a molecular weight of 300 or more such as 2-hydroxy-4-n-octoxybenzophenone and bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane. Is preferable because of a large value.
Further, the addition amount of the benzophenone compound is preferably about 0.05 to 1.5 parts by weight, more preferably 0.5 to 1.0 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
本発明では、前記したようなブタンテトラカルボン酸を有するヒンダードアミンとベンゾフェノン系化合物とを共に塩化ビニル系樹脂に配合することで、製膜（加熱成形）中ないし製膜直後に基材自体の黄変を引き起こすことがないうえ、従来品に比べ耐候性が飛躍的に向上したものとすることができる。
このようなヒンダードアミン系光安定剤とベンゾフェノン系紫外線吸収剤とを組み合わせた基材を用いれば、製膜（加熱成形）時の黄変が引き起こされないうえ、しかも、印刷物に貼着した後に紫外線などの光に長期に亘って晒されても、色やけ、退色などの色相変化が生じない印刷物保護フィルムの提供が可能となる。
In the present invention, the hindered amine having a butanetetracarboxylic acid as described above and a benzophenone-based compound are blended with a vinyl chloride resin, so that the base material itself turns yellow during film formation (thermoforming) or immediately after film formation. In addition, the weather resistance can be drastically improved compared to conventional products.
If such a base material that combines a hindered amine light stabilizer and a benzophenone ultraviolet absorber is used, yellowing during film formation (heat molding) is not caused, and ultraviolet light etc. is applied to the printed matter. It is possible to provide a printed matter protective film that does not cause a hue change such as color burn or fading even when exposed to light for a long time.
本発明では、熱安定剤として、バリウム−亜鉛系化合物を使用することが好ましい。カルシウム−亜鉛系やハイドロタルサイト系の安定剤では、製膜性に劣ることがある。
バリウム−亜鉛系化合物は、塩化ビニル系樹脂１００重量部に対し、３〜５重量部程度添加すればよいが、特に、前述の可塑剤の助剤であるエポキシ化大豆油と組み合わせて用いると、本発明の基材の製膜（成形加工）時における動的・静的熱安定性を高め、光に晒される前の黄変の発生を確実に抑える上で好適である。
In the present invention, it is preferable to use a barium-zinc compound as the heat stabilizer. Calcium-zinc and hydrotalcite stabilizers may be inferior in film forming properties.
The barium-zinc compound may be added in an amount of about 3 to 5 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. This is suitable for enhancing dynamic and static thermal stability during film formation (molding) of the substrate of the present invention and for reliably suppressing the occurrence of yellowing before exposure to light.
本発明の基材には、上記可塑剤、助剤、光安定剤、紫外線吸収剤、熱安定剤のほかに、必要に応じて、本発明の特性（透明性や製膜性、耐候性など）を損なわない範囲において、無機充填剤、顔料（着色剤）、酸化防止剤、難燃剤、滑剤などの各種添加剤を適宜添加することができる。 In addition to the plasticizers, auxiliaries, light stabilizers, UV absorbers, and heat stabilizers, the base material of the present invention may have the characteristics of the present invention (transparency, film-forming properties, weather resistance, etc.) as necessary. ) Can be added as appropriate to various additives such as inorganic fillers, pigments (colorants), antioxidants, flame retardants, and lubricants.
本発明の基材は、押出成形、カレンダー成形、インフレーション成形等の公知の手段によってフィルム状に加工することができる。
得られる基材の厚みについては、用途によって異なるが、６０〜３００μｍ程度が好ましく、より好ましくは６０〜１００μｍである。
The base material of the present invention can be processed into a film by known means such as extrusion molding, calendar molding, inflation molding and the like.
About the thickness of the obtained base material, although it changes with uses, about 60-300 micrometers is preferable, More preferably, it is 60-100 micrometers.
本発明の基材は、ＪＩＳ Ｋ７１０５に準じて測定される全光線透過率が８０％以上である。
全光線透過率が８０％未満のものでは、透明性に劣り、写真や紙類などの印刷物が視認しづらくなる虞があり、印刷物保護フィルムの基材として適さないことがある。
なお、上記所望の全光線透過率を得るために支障とならない範囲であれば、本発明の基材の表面（粘着層が形成されていない面）に、目的や用途などに応じて、マット感やシボ感を施してもよい。また、本発明の基材は、表面層や意匠層を有する多層構造としてもよい。
The base material of the present invention has a total light transmittance of 80% or more measured according to JIS K7105.
If the total light transmittance is less than 80%, the transparency is inferior, and printed matter such as photographs and papers may be difficult to visually recognize, which may not be suitable as a substrate for the printed matter protective film.
In addition, as long as it does not interfere with obtaining the desired total light transmittance, the surface of the substrate of the present invention (the surface on which the adhesive layer is not formed) has a matte feel depending on the purpose and application. You may give a feeling of wrinkles. Moreover, the base material of this invention is good also as a multilayer structure which has a surface layer and a design layer.
また、本発明の基材は、サンシャインウェザーメーターにおいて、ブラックパネル温度６３℃、６０分当たり１２分の水噴射の条件下、２０００時間経過した後の色相変化ΔＥ値が１．０以下であることが好ましく、より好ましくは０．５以下である。
上記条件下の促進試験における色相変化ΔＥ値が、１．０より高いものでは、例えば、５〜７年以上に亘って屋外で掲示される印刷物の保護フィルムなどに用いた場合に、変色が起こりやすくなる。
The base material of the present invention has a hue change ΔE value of 1.0 or less after 2000 hours in a sunshine weather meter under conditions of black panel temperature of 63 ° C. and water injection of 12 minutes per 60 minutes. Is preferable, and more preferably 0.5 or less.
When the hue change ΔE value in the accelerated test under the above conditions is higher than 1.0, for example, when used for a protective film of a printed matter posted outdoors for 5 to 7 years or more, discoloration occurs. It becomes easy.
以上のような本発明の基材に、粘着層を積層することで、印刷物保護フィルムとすることができる。
粘着層としては、本発明の特性（透明性や製膜性、耐候性など）を損なわないものであれば、特に限定されず、例えば、アクリル系粘着剤、シリコーン系粘着剤などから構成される。
A printed material protective film can be obtained by laminating an adhesive layer on the substrate of the present invention as described above.
The pressure-sensitive adhesive layer is not particularly limited as long as it does not impair the characteristics of the present invention (transparency, film-forming property, weather resistance, etc.), and is composed of, for example, an acrylic pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, or the like. .
実施例１〜７、比較例１〜４
表１に記載の配合処方にて、カレンダー成形により印刷物保護フィルム用基材として厚さ８０μｍのフィルムを得た。
なお、表１における各成分の数値は重量部である。
Examples 1-7, Comparative Examples 1-4
A film having a thickness of 80 μm was obtained as a substrate for a printed matter protective film by calendering with the formulation shown in Table 1.
In addition, the numerical value of each component in Table 1 is a weight part.
〔使用原料〕
・塩化ビニル系樹脂：重合度１０００のポリ塩化ビニル（塩化ビニルのホモポリマー）
・可塑剤：フタル酸ジオクチル
・光安定剤１：一般式（ＩＩ）で表されるブタンテトラカルボン酸を有するヒンダードアミン（分子量２０００）
・光安定剤２：一般式（Ｉ）で表されるブタンテトラカルボン酸を有するヒンダードアミン（分子量８４７）
・光安定剤３：ブタンテトラカルボン酸を有さないヒンダードアミン≪ビス（１−ウンデカノキシ−２，６，６，−テトラメチルピペラジン−４−イル）カルボネート（分子量６８１）≫
・紫外線吸収剤１：２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン（分子量３２６）
・紫外線吸収剤２：２−ヒドロキシ−４−メトキシベンゾフェノン（分子量２２８）
・紫外線吸収剤３：２−（２−ヒドロキシ−５−ｔ−オクチルフェニル）ベンゾトリアゾール（分子量３２３）
・熱安定剤１：バリウム−亜鉛系化合物
・熱安定剤２：カルシウム−亜鉛系化合物
・熱安定剤３：ハイドロタルサイト
[Raw materials]
・ Vinyl chloride resin: Polyvinyl chloride with a polymerization degree of 1000 (a homopolymer of vinyl chloride)
Plasticizer: Dioctyl phthalateLight stabilizer 1: Hindered amine having a butanetetracarboxylic acid represented by the general formula (II) (molecular weight 2000)
Light stabilizer 2: hindered amine having a butanetetracarboxylic acid represented by the general formula (I) (molecular weight 847)
Light stabilizer 3: hindered amine having no butanetetracarboxylic acid << bis (1-undecanoxy-2,6,6, -tetramethylpiperazin-4-yl) carbonate (molecular weight 681) >>
UV absorber 1: 2-hydroxy-4-n-octoxybenzophenone (molecular weight 326)
UV absorber 2: 2-hydroxy-4-methoxybenzophenone (molecular weight 228)
UV absorber 3: 2- (2-hydroxy-5-t-octylphenyl) benzotriazole (molecular weight 323)
-Heat stabilizer 1: Barium-zinc compound-Heat stabilizer 2: Calcium-zinc compound-Heat stabilizer 3: Hydrotalcite
上記実施例１〜７および比較例１〜４で得られたフィルムにつき、各特性を下記の評価方法で評価し、この結果を表１に併せて示す。 About the film obtained in the said Examples 1-7 and Comparative Examples 1-4, each characteristic was evaluated with the following evaluation method, and this result is combined with Table 1 and shown.
透明性
カレンダー成形後の各フィルムについて、ＪＩＳ Ｋ７１０５に準じて全光線透過率を測定し、全光線透過率が８０％以上である場合を「○」、８０％未満である場合を「×」とした。
Transparency For each film after calendering, the total light transmittance is measured in accordance with JIS K7105. When the total light transmittance is 80% or more, “◯”, and when it is less than 80%, “×”. did.
製膜性
カレンダー成形における製膜性を評価し、長時間安定してフィルムが得られる場合を「○」、長時間の製膜において、フィルムに若干の変色やヤケが生じる場合を「△」、フィルムの製膜自体が困難な場合を「×」とした。
Film-formability Evaluates the film-formability in calender molding, “○” when a film can be obtained stably for a long time, “△” when a film is slightly discolored or burned in a long-time film formation, The case where it was difficult to form the film itself was defined as “x”.
耐候性（色相変化ΔＥ）
縦５０ｍｍ×横５０ｍｍの評価サンプルを作成し、色彩色度計（ミノルタカメラ社製 商品名"ＣＲ−２００Ｂ"）を用い、ＪＩＳ Ｋ７３７３：２００６に準じて、サンプル表面の初期Ｅ値を測定した。
次いで、各サンプルに、スガ試験機の"３００サンシャインウェザーメーター"を使用して、ブラックパネル温度６３℃±３℃、６０分当たり１２分の水噴射の条件下、２０００時間経過した後のサンプル表面のＥ値を、初期Ｅ値と同様に測定し、初期Ｅ値との差をΔＥ値として求め、ΔＥ値が１．０未満を「○」、１．０以上２．０未満を「△」２．０以上を「×」と評価した。なお、このΔＥ値は、色の変化具合を数字化したものであり、値が小さい方が、色の変化（黄変）が少ないことを示す。
Weather resistance (hue change ΔE)
An evaluation sample having a length of 50 mm and a width of 50 mm was prepared, and an initial E value of the sample surface was measured using a chromaticity meter (trade name “CR-200B” manufactured by Minolta Camera Co., Ltd.) according to JIS K7373: 2006.
Then, using each of the samples, the surface of the sample after 2000 hours under the conditions of a black panel temperature of 63 ° C. ± 3 ° C. and a water injection of 12 minutes per 60 minutes using a “300 Sunshine Weather Meter” of Suga Test Instruments The E value is measured in the same manner as the initial E value, and the difference from the initial E value is obtained as a ΔE value. 2.0 or more was evaluated as "x". The ΔE value is obtained by digitizing the degree of color change. A smaller value indicates a smaller color change (yellowing).
なお、比較例４のフィルムは、透明性や製膜性、耐候性については問題無いものの、コシに劣り、印刷物保護フィルム用途には向かないものであった。 In addition, although the film of the comparative example 4 was satisfactory about transparency, film forming property, and a weather resistance, it was inferior to stiffness and was not suitable for printed matter protective film use.
本発明の基材は、基材自体の変色がなく、優れた透明性を有しながら、耐候性なども兼ね備えているので、印刷物を保護するためのフィルム用途に非常に有効である。
このような本発明の基材を用いた印刷物保護フィルムによってラミネートされた印刷物は、例えば、屋内や屋外での各種広告、表示、看板などとして好適に使用され得る。
The base material of the present invention is very effective for film use for protecting printed matter because the base material itself has no discoloration and has excellent transparency and weather resistance.
The printed matter laminated with the printed matter protective film using the base material of the present invention can be suitably used as, for example, various advertisements, displays, signboards, and the like indoors and outdoors.
Claims (3)
塩化ビニル系樹脂１００重量部に対し、１０〜３０重量部の可塑剤と、
光安定剤として、ブタンテトラカルボン酸を有するヒンダードアミン、
紫外線吸収剤として、ベンゾフェノン系化合物
とを含んでなり、かつＪＩＳ Ｋ７１０５に準じて測定される全光線透過率が８０％以上であることを特徴とする印刷物保護フィルム用基材。 A film substrate for protecting printed matter,
10 to 30 parts by weight of a plasticizer with respect to 100 parts by weight of the vinyl chloride resin;
As a light stabilizer, a hindered amine having butanetetracarboxylic acid,
A substrate for a printed matter protective film comprising a benzophenone-based compound as an ultraviolet absorber and having a total light transmittance of 80% or more measured according to JIS K7105.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014161143A JP6400976B2 (en) | 2014-08-07 | 2014-08-07 | Base material for printed matter protection film |
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| Application Number | Priority Date | Filing Date | Title |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0270711A (en) * | 1988-09-06 | 1990-03-09 | Adeka Argus Chem Co Ltd | Vinyl chloride resin composition for agricultural use |
| JPH05278168A (en) * | 1992-02-28 | 1993-10-26 | Minnesota Mining & Mfg Co <3M> | Adhesive film or sheet |
| JPH06145450A (en) * | 1992-11-10 | 1994-05-24 | Sekisui Chem Co Ltd | Vinyl chloride-based resin composition |
| JPH077522A (en) * | 1991-04-04 | 1995-01-10 | Nippon Telegr & Teleph Corp <Ntt> | Node bypass reporting method |
| JPH0770522A (en) * | 1993-09-03 | 1995-03-14 | Sekisui Chem Co Ltd | Protective adhesive film |
| JPH09309996A (en) * | 1996-05-22 | 1997-12-02 | Achilles Corp | Agricultural vinyl chloride resin film |
| JP2001316490A (en) * | 2000-02-28 | 2001-11-13 | Achilles Corp | Vinyl chloride resin film |
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2014
- 2014-08-07 JP JP2014161143A patent/JP6400976B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0270711A (en) * | 1988-09-06 | 1990-03-09 | Adeka Argus Chem Co Ltd | Vinyl chloride resin composition for agricultural use |
| JPH077522A (en) * | 1991-04-04 | 1995-01-10 | Nippon Telegr & Teleph Corp <Ntt> | Node bypass reporting method |
| JPH05278168A (en) * | 1992-02-28 | 1993-10-26 | Minnesota Mining & Mfg Co <3M> | Adhesive film or sheet |
| JPH06145450A (en) * | 1992-11-10 | 1994-05-24 | Sekisui Chem Co Ltd | Vinyl chloride-based resin composition |
| JPH0770522A (en) * | 1993-09-03 | 1995-03-14 | Sekisui Chem Co Ltd | Protective adhesive film |
| JPH09309996A (en) * | 1996-05-22 | 1997-12-02 | Achilles Corp | Agricultural vinyl chloride resin film |
| JP2001316490A (en) * | 2000-02-28 | 2001-11-13 | Achilles Corp | Vinyl chloride resin film |
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| JP6400976B2 (en) | 2018-10-03 |
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