TW202100678A - Coating liquid for paper and coated paper using same - Google Patents

Coating liquid for paper and coated paper using same Download PDF

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Publication number
TW202100678A
TW202100678A TW109112453A TW109112453A TW202100678A TW 202100678 A TW202100678 A TW 202100678A TW 109112453 A TW109112453 A TW 109112453A TW 109112453 A TW109112453 A TW 109112453A TW 202100678 A TW202100678 A TW 202100678A
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ethylene
paper
vinyl alcohol
mass
alcohol copolymer
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TW109112453A
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Chinese (zh)
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谷田達也
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日商可樂麗股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Abstract

This coating liquid for paper contains an ethylene-vinyl alcohol copolymer (A) and an alkali metal salt (B) of carboxylic acid, wherein: the content of an ethylene unit in the ethylene-vinyl alcohol copolymer (A) is 1-20 mol% (exclusive of 20); the degree of crystallinity Cw(30 DEG C) in water at 30 DEG C and the degree of crystallinity Cw(70 DEG C) in water at 70 DEG C, as measured by pulsed NMR, satisfy the formula (I); and the alkali metal salt (B) of carboxylic acid is contained in an amount of 0.001-1 part by mass, in terms of the mass of alkali metal, with respect to 100 parts by mass of the ethylene-vinyl alcohol copolymer (A). Consequently, provided is a coating liquid for paper having excellent water resistance and excellent barrier properties.

Description

紙用塗覆液及使用其之塗覆紙Coating liquid for paper and coated paper using it

本發明關於含有乙烯-乙烯醇共聚物之紙用塗覆液。又，關於使用其之塗覆紙及剝離紙。再者，本案主張西元2019年4月15日申請的日本發明專利申請案第2019-077137號之優先權，藉由參照其全體而作為本申請案之一部分引用。The present invention relates to a coating liquid for paper containing an ethylene-vinyl alcohol copolymer. Also, about the coated paper and release paper using it. Furthermore, this case claims the priority of Japanese Invention Patent Application No. 2019-077137 filed on April 15, 2019, and is cited as a part of this application by referring to the entirety.

聚乙烯醇(以下亦簡稱「PVA」)係已知作為水溶性的合成高分子，廣泛使用於合成纖維之尼綸的原料、紙加工劑、纖維加工劑、接著劑、乳化聚合及懸浮聚合用之安定劑、無機物之黏結劑、薄膜等用途。特別地，已知藉由將PVA塗布於紙，可賦予紙力增強、耐水化、耐油化、阻氣性等，而被廣泛利用。又，PVA亦作為無機之黏結劑或分散安定劑、對紙的功能性賦予之助劑使用。Polyvinyl alcohol (hereinafter also referred to as "PVA") is known as a water-soluble synthetic polymer and is widely used as a raw material for synthetic fiber nylon, paper processing agent, fiber processing agent, adhesive, emulsion polymerization and suspension polymerization It is used as stabilizer, bonding agent for inorganic substances, and film. In particular, it is known that by coating PVA on paper, it can provide paper strength enhancement, water resistance, oil resistance, gas barrier properties, etc., and it is widely used. In addition, PVA is also used as an inorganic binder, dispersion stabilizer, and auxiliary agent for imparting paper functionality.

於塗覆紙之中，尤其於剝離紙中，以減少構成紙的紙漿纖維間之空隙，提高塗布於紙表面的聚矽氧之表面良率為目的，一般使用PVA作為填隙層(阻隔層)。其中，已知部分皂化PVA係阻隔性優異。In coated paper, especially in release paper, to reduce the voids between the pulp fibers constituting the paper and improve the surface yield of the polysiloxane coated on the paper surface, PVA is generally used as the interstitial layer (barrier layer) ). Among them, it is known that the partially saponified PVA system has excellent barrier properties.

然而，部分皂化PVA由於耐水性差，故因黏著加工步驟等中之加濕而PVA溶出，有黏連之問題。再者，有於後加工步驟中無法使用水分散清漆之問題。However, partially saponified PVA has poor water resistance, so the PVA is eluted due to humidification in the adhesion processing step, and there is a problem of adhesion. Furthermore, there is a problem that water-dispersible varnish cannot be used in post-processing steps.

對於上述問題，專利文獻1中記載藉由使用乙烯-乙烯醇共聚物與羧甲基纖維素之混合物，而可兼顧阻隔性與耐水性。Regarding the above problems, Patent Document 1 describes that by using a mixture of ethylene-vinyl alcohol copolymer and carboxymethyl cellulose, both barrier properties and water resistance can be achieved.

然而，該乙烯-乙烯醇共聚物由於包含疏水性的乙烯單元，故水中的溶解性比未改質的PVA更低，於調製水溶液之際有發生溶渣(以下亦簡稱「不溶分」。)之情況。另一方面，若為了抑制不溶分之生成而降低皂化度，則有在溶解時粒子彼此凝聚而成為粉塊之情況。使用含有不溶分或粉塊的水溶液作為紙用塗覆液時，由於彼等成為塗覆面的微小缺點而有阻隔性減低之情況。 [先前技術文獻] [專利文獻]However, since this ethylene-vinyl alcohol copolymer contains hydrophobic ethylene units, the solubility in water is lower than that of unmodified PVA, and slag (hereinafter also referred to as "insoluble matter") occurs when the aqueous solution is prepared. The situation. On the other hand, if the degree of saponification is lowered in order to suppress the formation of insolubles, the particles may agglomerate with each other during dissolution to form agglomerates. When an aqueous solution containing insoluble components or powdery lumps is used as a coating liquid for paper, the barrier properties may be reduced due to the minor defects of the coated surface. [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本特開平11-21788號公報[Patent Document 1] JP 11-21788 A

[發明欲解決之課題][The problem to be solved by the invention]

本發明係為了解決上述課題而完成者，目的在於提供包含乙烯-乙烯醇共聚物之紙用塗覆液。而且，目的在於藉由使用該紙用塗覆液，而提供耐水性及阻隔性優異之塗覆紙及剝離紙。 [用以解決課題之手段]The present invention was accomplished in order to solve the above-mentioned problems, and the object is to provide a coating liquid for paper containing an ethylene-vinyl alcohol copolymer. Furthermore, the purpose is to provide coated paper and release paper excellent in water resistance and barrier properties by using the coating liquid for paper. [Means to solve the problem]

上述課題係藉由提供一種紙用塗覆液而解決，其係包含乙烯-乙烯醇共聚物(A)及羧酸的鹼金屬鹽(B)之紙用塗覆液；前述乙烯-乙烯醇共聚物(A)的乙烯單元之含有率為1莫耳%以上且小於20莫耳%，以脈衝NMR求出之在30℃的水中結晶化度Cw(30℃)及在70℃的水中結晶化度Cw(70℃)滿足下述式(I)，且相對於100質量份的前述乙烯-乙烯醇共聚物(A)，以鹼金屬的質量換算含有0.001～1質量份的前述羧酸的鹼金屬鹽(B)。The above problem is solved by providing a paper coating liquid, which is a paper coating liquid containing an ethylene-vinyl alcohol copolymer (A) and an alkali metal salt of a carboxylic acid (B); the aforementioned ethylene-vinyl alcohol copolymer The content of the ethylene unit of the substance (A) is 1 mol% or more and less than 20 mol%, the degree of crystallinity Cw (30°C) in water at 30°C and crystallization in water at 70°C obtained by pulse NMR The degree Cw (70°C) satisfies the following formula (I), and contains 0.001 to 1 part by mass of the carboxylic acid based on the mass of the alkali metal relative to 100 parts by mass of the ethylene-vinyl alcohol copolymer (A) Metal salt (B).

Figure 02_image001
Figure 02_image001

此時，前述乙烯-乙烯醇共聚物(A)之黏度平均聚合度較佳為900～2400。又，前述乙烯-乙烯醇共聚物(A)之皂化度亦較佳為90～98.5莫耳%。At this time, the viscosity average polymerization degree of the aforementioned ethylene-vinyl alcohol copolymer (A) is preferably 900-2400. In addition, the saponification degree of the aforementioned ethylene-vinyl alcohol copolymer (A) is also preferably 90-98.5 mol%.

上述課題亦藉由提供一種將前述塗覆液塗布於紙之表面而成的塗覆紙所解決。此時，該塗覆紙之合適實施態樣為剝離紙原紙。又，在將前述塗覆液塗布於紙上而形成的填隙層之上，形成剝離層而成之剝離紙亦為合適實施態樣。此時，剝離層較佳為包含聚矽氧樹脂。 [發明之效果]The above problem is also solved by providing a coated paper obtained by coating the aforementioned coating liquid on the surface of the paper. At this time, a suitable implementation aspect of the coated paper is a release paper base paper. In addition, a release paper obtained by forming a release layer on the interstitial layer formed by applying the coating liquid on paper is also a suitable implementation aspect. In this case, the release layer preferably contains silicone resin. [Effects of Invention]

塗布有本發明之塗覆液的塗覆紙係阻隔性、耐水性優異。因此，適用於剝離紙。再者，本發明之紙用塗覆液係藉由優異的耐水性，而抗黏連性亦優異，同時可在後加工步驟中使用水分散性清漆。The coated paper coated with the coating liquid of the present invention has excellent barrier properties and water resistance. Therefore, it is suitable for release paper. Furthermore, the coating liquid for paper of the present invention has excellent water resistance and excellent blocking resistance. At the same time, a water-dispersible varnish can be used in post-processing steps.

[用以實施發明的形態][Form to implement the invention]

本發明之紙用塗覆液係包含乙烯-乙烯醇共聚物(A)及羧酸的鹼金屬鹽(B)之塗覆液；其特徵為：該乙烯-乙烯醇共聚物(A)的乙烯單元之含有率為1莫耳%以上且小於20莫耳%，以脈衝NMR求出之在30℃的水中結晶化度Cw(30℃)及在70℃的水中結晶化度Cw(70℃)滿足下述式(I)，且相對於100質量份的前述乙烯-乙烯醇共聚物(A)，以鹼金屬的質量換算含有0.001～1質量份的前述羧酸的鹼金屬鹽(B)。The coating liquid for paper of the present invention is a coating liquid containing an ethylene-vinyl alcohol copolymer (A) and an alkali metal salt of a carboxylic acid (B); it is characterized in that the ethylene-vinyl alcohol copolymer (A) is ethylene The content of the unit is 1 mol% or more and less than 20 mol%. The crystallinity degree Cw (30℃) in water at 30℃ and the crystallinity degree Cw (70℃) in water at 70℃ calculated by pulse NMR It satisfies the following formula (I) and contains 0.001 to 1 part by mass of the alkali metal salt of the carboxylic acid (B) in terms of the mass of the alkali metal relative to 100 parts by mass of the ethylene-vinyl alcohol copolymer (A).

Figure 02_image001
Figure 02_image001

[乙烯-乙烯醇共聚物(A)] 本發明之紙用塗覆液中所含有的乙烯-乙烯醇共聚物(A)係特徵為：乙烯單元之含有率為1莫耳%以上且小於20莫耳%，以脈衝NMR(核磁共振吸收法)求出之在30℃的水中結晶化度Cw(30℃)與在70℃的水中結晶化度Cw(70℃)滿足上述式(I)。關於此點，以下說明。[Ethylene-vinyl alcohol copolymer (A)] The ethylene-vinyl alcohol copolymer (A) contained in the coating liquid for paper of the present invention is characterized in that the content of ethylene units is 1 mol% or more and less than 20 mol%, and pulse NMR (nuclear magnetic resonance absorption) Method) The obtained crystallization degree Cw (30°C) in water at 30°C and the crystallization degree Cw (70°C) in water at 70°C satisfy the above formula (I). On this point, the following explains.

(水中結晶化度) 首先，說明藉由脈衝NMR測定聚合物試料之意義。於脈衝NMR裝置中存在因裝置中的電磁鐵所產生的靜磁場。於靜磁場中氫核之核自旋的方向係配向於與靜磁場相同方向。於此，若給予脈衝磁場，則氫核之核自旋從靜磁場方向成為倒90°的激發狀態。然後，將經激發的核自旋之方向在巨觀上回到原來的靜磁場方向之過程稱為T2 緩和或橫緩和，將此過程所需要的時間稱為緩和時間(Tau)。於單一成分之緩和時，時間(t)中的磁化強度(y)係使用激發狀態下的緩和強度(A)、緩和時間(Tau)及常數(y0 、W)，用以下之式(II)表示。再者，W為韋伯係數，W=1時式(II)係成為Exp型，W=2時成為高斯(Gauss)型。一般的聚合物試料之情況為1≦W≦2。(The degree of crystallinity in water) First, the significance of measuring polymer samples by pulse NMR is explained. In a pulsed NMR device, there is a static magnetic field generated by the electromagnet in the device. The direction of the nuclear spins of hydrogen nuclei in the static magnetic field is aligned in the same direction as the static magnetic field. Here, if a pulsed magnetic field is applied, the nuclear spins of the hydrogen nuclei become excited 90° from the direction of the static magnetic field. Then, the process of macroscopically returning the direction of the excited nuclear spins to the original static magnetic field direction is called T 2 relaxation or horizontal relaxation, and the time required for this process is called relaxation time (Tau). In the relaxation of a single component, the magnetization (y) in time (t) is based on the relaxation intensity (A), relaxation time (Tau) and constants (y 0 , W) in the excited state, and the following formula (II) ) Means. Furthermore, W is the Weber coefficient. When W=1, the formula (II) becomes Exp type, and when W=2, it becomes Gauss type. The case of a general polymer sample is 1≦W≦2.

Figure 02_image005
Figure 02_image005

於T2 緩和時，氫核係一邊與其它氫核進行能量交換，一邊衰減。因此，於試料的分子運動性高時，由於與相互接近的質子之相互作用小，全體之能量衰減不易發生，緩和時間變長。另一方面，於分子運動性低時，緩和時間變短。因此，若為結晶性聚合物材料，則在結晶部中緩和時間短，在非晶部中緩和時間變長。於實際的結晶性聚合物中，存在結晶部與非晶部，於其緩和曲線中來自緩和時間短的結晶部之緩和成分與來自緩和時間長的非晶部由來之緩和成分之和係被觀測。將來自結晶部的緩和強度當作A1 ，將來自非晶部的緩和強度當作A2 ，將來自結晶部的緩和時間當作Tau1 ，將來自非晶部的緩和時間當作Tau2 時，時間(t)的試料全體之磁化強度(y)係使用常數(y0 )，用以下之式(III)表示。再者，y0 係源自從測定裝置而來的熱雜訊之成分，為依賴於時間t之參數，由於不影響緩和強度(A1 )及(A2 )之值，水中結晶化度(Cw)係不受到y0 之影響。結晶成分由顯示Gauss型緩和者多，故於表示式(III)的結晶成分之第1項中，在W=2固定。由此式所導出的A1 /(A1 +A2 )係藉由脈衝NMR所得之結晶化度。於本說明書中，於使用脈衝NMR之測定中，使用被稱為Solid-echo法之脈衝序列。When T 2 relaxes, the hydrogen nucleus system decays while exchanging energy with other hydrogen nuclei. Therefore, when the molecular mobility of the sample is high, since the interaction with the protons close to each other is small, the overall energy attenuation is less likely to occur, and the relaxation time becomes longer. On the other hand, when the molecular mobility is low, the relaxation time becomes shorter. Therefore, in the case of a crystalline polymer material, the relaxation time is short in the crystalline part, and the relaxation time is long in the amorphous part. In actual crystalline polymers, there are crystalline parts and amorphous parts. In the relaxation curve, the sum of the relaxation component from the crystal part with a short relaxation time and the relaxation component derived from the amorphous part with a long relaxation time is observed. . When taking the relaxation strength from the crystalline part as A 1 , the relaxation strength from the amorphous part as A 2 , the relaxation time from the crystal part as Tau 1 , and the relaxation time from the amorphous part as Tau 2 , The magnetization (y) of the entire sample at time (t) is represented by the following formula (III) using a constant (y 0 ). Furthermore, y 0 is a component derived from the thermal noise from the measuring device. It is a parameter that depends on the time t. Since it does not affect the values of the relaxation intensity (A 1 ) and (A 2 ), the degree of crystallinity in water ( Cw) is not affected by y 0 . There are many crystalline components that show Gauss-type relaxation. Therefore, in the first term of the crystalline component of the formula (III), W=2 is fixed. A 1 /(A 1 +A 2 ) derived from this formula is the degree of crystallinity obtained by pulse NMR. In this specification, in the measurement using pulsed NMR, a pulse sequence called the Solid-echo method is used.

Figure 02_image007
Figure 02_image007

如以上，可由以脈衝NMR測定的緩和曲線來得到聚合物試料中的結晶成分與非晶成分之比例。乙烯-乙烯醇共聚物係具有多數的羥基之親水性聚合物，在水中膨潤而結晶化度降低，但其程度係大幅受到水溫之影響。若水溫變高，則膨潤度變大，結果結晶化度降低。於本發明中，著眼於以脈衝NMR求出之在30℃的水中結晶化度Cw(30℃)(%)及在70℃的水中結晶化度Cw(70℃)(%)。此時，雖然乙烯-乙烯醇共聚物(A)為水溶性聚合物，但為了暫時使結晶化的乙烯-乙烯醇共聚物(A)溶解於水中，必須高溫之條件或攪拌操作。因此，於30℃或70℃之水中靜置的程度，試料係不溶解而只有膨潤，以固體之狀態存在。因此，於上述脈衝NMR測定中以固體狀態進行測定。As described above, the ratio of the crystalline component to the amorphous component in the polymer sample can be obtained from the transition curve measured by pulse NMR. Ethylene-vinyl alcohol copolymer is a hydrophilic polymer with many hydroxyl groups. It swells in water and reduces the degree of crystallinity, but its degree is greatly affected by water temperature. As the water temperature becomes higher, the degree of swelling becomes larger, and as a result, the degree of crystallinity decreases. In the present invention, attention is paid to the degree of crystallinity Cw (30°C) (%) in water at 30°C and the degree of crystallinity Cw (70°C) (%) in water at 70°C obtained by pulse NMR. At this time, although the ethylene-vinyl alcohol copolymer (A) is a water-soluble polymer, in order to temporarily dissolve the crystallized ethylene-vinyl alcohol copolymer (A) in water, high-temperature conditions or stirring operations are required. Therefore, the sample does not dissolve but only swells to the extent that it is left standing in water at 30°C or 70°C, and exists in a solid state. Therefore, the measurement is performed in a solid state in the above-mentioned pulse NMR measurement.

本發明之乙烯-乙烯醇共聚物(A)滿足下述式(I)。此處，水中結晶化度(Cw)不是以緩和時間之絕對值來決定，而是藉由將系統分割成緩和時間不同的2成分後各自之比率的緩和強度(A1 )及(A2 )所決定之參數。此緩和強度(A1 )及(A2 )由於不受共振頻率之變化所影響，故水中結晶化度(Cw)之值不受到共振頻率之影響。The ethylene-vinyl alcohol copolymer (A) of the present invention satisfies the following formula (I). Here, the degree of crystallinity in water (Cw) is not determined by the absolute value of the relaxation time, but by dividing the system into 2 components with different relaxation times and the respective ratios of the relaxation strength (A 1 ) and (A 2 ) The determined parameter. Since the relaxation strength (A 1 ) and (A 2 ) are not affected by the change of resonance frequency, the value of crystallinity (Cw) in water is not affected by the resonance frequency.

Figure 02_image001
Figure 02_image001

上述式(I)中，[(100-Cw(30℃))/100]表示30℃的非晶部之比率，取0～1之值。又，[Cw(30℃)-Cw(70℃)]係30℃與70℃的水中結晶化度之差，亦即隨著水溫上升而非晶部增加量之指標，取0～100之值。因此，將此等相乘後的式(I)係乙烯-乙烯醇共聚物(A)的易溶解性之指標，於式(I)之值中，絕對值大的[Cw(30℃)-Cw(70℃)]者係大幅影響。通常乙烯單元之含有率為1莫耳%以上且小於20莫耳%之乙烯-乙烯醇共聚物，由於乙烯單元之含有率少，因此溶解於水。如此的水溶性之乙烯-乙烯醇共聚物通常由於[(100-Cw(30℃))/100]之值大且[Cw(30℃)-Cw(70℃)]之值小，結果有式(I)之值變小之情況，及由於[(100-Cw(30℃))/100]之值小且[Cw(30℃)-Cw(70℃)]之值大，結果有式(I)之值變大之情況。即，式(I)之值小於4時，在低溫下易溶解，但另一方面容易成為粉塊，再者因一旦生成的粉塊難以溶解於水，到完全溶解的溶解時間變長。式(I)之下限較佳為5以上，更佳為6以上。另一方面，式(I)之值超過22時，在水中的溶解性降低，到完全溶解的溶解時間變長。式(I)之上限較佳為21以下，更佳為20以下。由於上述式(I)滿足特定之範圍，得到溶解速度快且在溶解時不易成為粉塊之乙烯-乙烯醇共聚物(A)。In the above formula (I), [(100-Cw(30°C))/100] represents the ratio of the amorphous portion at 30°C, taking a value of 0 to 1. In addition, [Cw(30℃)-Cw(70℃)] is the difference in crystallinity between 30℃ and 70℃, that is, as the water temperature rises, the index of the increase of the non-crystalline part, which is 0-100 value. Therefore, the formula (I) after multiplying these is an index of the easy solubility of the ethylene-vinyl alcohol copolymer (A). Among the values of the formula (I), the absolute value of [Cw(30°C)- Cw (70℃)] is greatly affected. Generally, an ethylene-vinyl alcohol copolymer with an ethylene unit content of 1 mol% or more and less than 20 mol% is dissolved in water because the ethylene unit content is low. Such a water-soluble ethylene-vinyl alcohol copolymer usually has a large value of [(100-Cw(30℃))/100] and a small value of [Cw(30℃)-Cw(70℃)], resulting in the formula When the value of (I) becomes small, and because the value of [(100-Cw(30℃))/100] is small and the value of [Cw(30℃)-Cw(70℃)] is large, the result is the formula ( The value of I) becomes larger. That is, when the value of the formula (I) is less than 4, it is easy to dissolve at low temperature, but on the other hand, it is easy to become a powder lump. Furthermore, since the powder lump once formed is difficult to dissolve in water, the dissolution time to complete dissolution becomes longer. The lower limit of formula (I) is preferably 5 or more, more preferably 6 or more. On the other hand, when the value of formula (I) exceeds 22, the solubility in water decreases, and the dissolution time to complete dissolution becomes longer. The upper limit of the formula (I) is preferably 21 or less, more preferably 20 or less. Since the above formula (I) satisfies the specific range, the ethylene-vinyl alcohol copolymer (A) is obtained which has a fast dissolution rate and does not easily become a powder when dissolving.

於測定時，將乙烯-乙烯醇共聚物(A)之試料靜置於各溫度(30℃、70℃)的H2 O-d2 中40分鐘後，於與靜置時的溫度相同之溫度下進行脈衝NMR測定。以上述式(III)，使用誤差最小平方法來擬合所得之緩和曲線的0～0.8ms之範圍。During the measurement, the sample of the ethylene-vinyl alcohol copolymer (A) was placed in H 2 Od 2 at each temperature (30°C, 70°C) for 40 minutes, and then carried out at the same temperature as the standing temperature Pulsed NMR measurement. Using the above formula (III), the error least square method is used to fit the range of 0-0.8 ms of the obtained relaxation curve.

滿足上述式(I)的乙烯-乙烯醇共聚物(A)係在溶解於水中時，由於來自粉塊的不溶物或凝聚物之生成少，例如，使用乙烯-乙烯醇共聚物(A)作為乳化聚合安定劑，將乙烯性不飽和單體予以乳化聚合，可得到凝聚物之生成少、耐水接著性及造膜性優異之水性乳液。The ethylene-vinyl alcohol copolymer (A) that satisfies the above formula (I) is dissolved in water, because the formation of insoluble matter or agglomerates from the powder is small, for example, the ethylene-vinyl alcohol copolymer (A) is used as Emulsion polymerization stabilizer, the ethylenically unsaturated monomer is emulsified and polymerized to obtain an aqueous emulsion with less formation of agglomerates, excellent water resistance and film forming properties.

滿足上述式(I)的乙烯-乙烯醇共聚物(A)係可藉由包含聚合步驟、皂化步驟、粉碎步驟、脫液步驟及乾燥步驟之特別的乙烯-乙烯醇共聚物之製造方法而得。關於該製造方法，以後詳細地說明。於本發明中，藉由採用如此之特別的製造方法，初次能得到滿足上述式(I)、在水中的溶解性優異之乙烯-乙烯醇共聚物(A)。以下，更詳細地說明乙烯-乙烯醇共聚物(A)。The ethylene-vinyl alcohol copolymer (A) that satisfies the above formula (I) can be obtained by a special ethylene-vinyl alcohol copolymer manufacturing method including a polymerization step, a saponification step, a pulverization step, a deliquoring step, and a drying step . This manufacturing method will be described in detail later. In the present invention, by adopting such a special production method, an ethylene-vinyl alcohol copolymer (A) that satisfies the above formula (I) and is excellent in water solubility can be obtained for the first time. Hereinafter, the ethylene-vinyl alcohol copolymer (A) will be described in more detail.

(乙烯酯) 乙烯-乙烯醇共聚物(A)係包含將乙烯與乙烯酯共聚合所得之乙烯-乙烯酯共聚物予以皂化之步驟而得。作為所用的乙烯酯，可舉出甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、戊酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、苯甲酸乙烯酯、三甲基乙酸乙烯酯及新癸酸乙烯酯等，其中較佳為乙酸乙烯酯。(Vinyl ester) The ethylene-vinyl alcohol copolymer (A) is obtained by saponifying an ethylene-vinyl ester copolymer obtained by copolymerizing ethylene and vinyl ester. The vinyl esters used include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl decanoate, vinyl laurate, vinyl stearate, vinyl benzoate, trimethyl Among them, vinyl acetate, vinyl neodecanoate, etc. are preferably vinyl acetate.

(乙烯單元之含有率) 乙烯-乙烯醇共聚物(A)的乙烯單元之含有率為1莫耳%以上且小於20莫耳%。乙烯單元之含有率小於1莫耳%時，所得之水性乳液的耐水接著性降低。乙烯單元之含有率較佳為1.5莫耳%以上，更佳為2莫耳%以上。另一方面，乙烯單元之含有率為20莫耳%以上時，乙烯-乙烯醇共聚物(A)變成不溶於水，水溶液之調製變困難。乙烯單元之含有率較佳為15莫耳%以下，更佳為10莫耳%以下，尤佳為8.5莫耳%以下。(Content rate of ethylene unit) The ethylene unit content of the ethylene-vinyl alcohol copolymer (A) is 1 mol% or more and less than 20 mol%. When the ethylene unit content is less than 1 mol%, the water-resistant adhesiveness of the resulting aqueous emulsion is reduced. The content of the ethylene unit is preferably 1.5 mol% or more, more preferably 2 mol% or more. On the other hand, when the content rate of the ethylene unit is 20 mol% or more, the ethylene-vinyl alcohol copolymer (A) becomes insoluble in water, and the preparation of the aqueous solution becomes difficult. The content of the ethylene unit is preferably 15 mol% or less, more preferably 10 mol% or less, and particularly preferably 8.5 mol% or less.

乙烯單元之含有率例如係由乙烯-乙烯醇共聚物(A)之前驅物或再乙醯化物的乙烯-乙烯酯共聚物之1 H-NMR求出。使用正己烷與丙酮的混合溶液，進行3次以上的試料的乙烯-乙烯酯共聚物之再沈澱純化後，在80℃下減壓乾燥3日而製作分析用的乙烯-乙烯酯共聚物。將分析用的乙烯-乙烯酯共聚物溶解於DMSO-d6 中，在80℃測定1 H-NMR(500MHz)。使用源自乙烯酯的主鏈次甲基之波峰(4.7～5.2ppm)與源自乙烯及乙烯酯的主鏈亞甲基之波峰(0.8～1.6ppm)，可算出乙烯單元之含有率。The content of ethylene units is determined, for example, from 1 H-NMR of an ethylene-vinyl ester copolymer of an ethylene-vinyl alcohol copolymer (A) precursor or re-acetate. Using a mixed solution of n-hexane and acetone, the sample ethylene-vinyl ester copolymer was reprecipitated and purified three times or more, and then dried under reduced pressure at 80°C for 3 days to prepare an ethylene-vinyl ester copolymer for analysis. The ethylene-vinyl ester copolymer for analysis was dissolved in DMSO-d 6 and 1 H-NMR (500 MHz) was measured at 80°C. Using the peak (4.7-5.2 ppm) of the main chain methine derived from vinyl ester and the peak (0.8-1.6 ppm) of the main chain methylene derived from ethylene and vinyl ester, the content rate of the ethylene unit can be calculated.

(皂化度) 乙烯-乙烯醇共聚物(A)之皂化度係沒有特別的限制，但較佳為80～99.99莫耳%。皂化度小於80莫耳%時，所得之水溶液中的乙烯-乙烯醇共聚物(A)之溶解性變不充分。皂化度更佳為82莫耳%以上，尤佳為85莫耳%以上，特佳為90%以上。另一方面，皂化度超過99.99莫耳%時，有難以安定地製造乙烯-乙烯醇共聚物(A)之傾向。皂化度更佳為99.5莫耳%以下，尤佳為99莫耳%以下，特佳為98.5莫耳%以下。乙烯-乙烯醇共聚物(A)之皂化度係可依據JIS K6726(1994年)進行測定。(Degree of saponification) The saponification degree of the ethylene-vinyl alcohol copolymer (A) is not particularly limited, but is preferably 80-99.99 mol%. When the degree of saponification is less than 80 mol%, the solubility of the ethylene-vinyl alcohol copolymer (A) in the resulting aqueous solution becomes insufficient. The degree of saponification is more preferably 82 mol% or more, particularly preferably 85 mol% or more, and particularly preferably 90% or more. On the other hand, when the saponification degree exceeds 99.99 mol%, it tends to be difficult to produce the ethylene-vinyl alcohol copolymer (A) stably. The degree of saponification is more preferably 99.5 mol% or less, particularly preferably 99 mol% or less, and particularly preferably 98.5 mol% or less. The saponification degree of the ethylene-vinyl alcohol copolymer (A) can be measured in accordance with JIS K6726 (1994).

(黏度平均聚合度) 乙烯-乙烯醇共聚物(A)之黏度平均聚合度係沒有特別的限制，但較佳為200～5000。黏度平均聚合度小於200時，所得之水性乳液的保管安定性降低。黏度平均聚合度較佳為250以上，更佳為300以上，尤佳為400以上，特佳為900以上。另一方面，黏度平均聚合度超過5000時，乙烯-乙烯醇共聚物水溶液之黏度變過高，有操作變困難之傾向。黏度平均聚合度較佳為4500以下，更佳為4000以下，尤佳為3500以下，特佳為2400以下。黏度平均聚合度P係可依據JIS K6726(1994年)進行測定。即，可將乙烯-乙烯醇共聚物(A)再皂化到皂化度99.5莫耳%以上而純化後，由在30℃的水中所測定的極限黏度[η](L/g)，藉由下式求出。 P=([η]×10000/8.29)(1/0.62) (Viscosity average degree of polymerization) The viscosity average degree of polymerization of the ethylene-vinyl alcohol copolymer (A) is not particularly limited, but is preferably 200 to 5,000. When the viscosity average degree of polymerization is less than 200, the storage stability of the resulting aqueous emulsion decreases. The viscosity average degree of polymerization is preferably 250 or more, more preferably 300 or more, particularly preferably 400 or more, and particularly preferably 900 or more. On the other hand, when the viscosity average polymerization degree exceeds 5000, the viscosity of the ethylene-vinyl alcohol copolymer aqueous solution becomes too high, and the handling tends to become difficult. The viscosity average degree of polymerization is preferably 4500 or less, more preferably 4000 or less, particularly preferably 3,500 or less, and particularly preferably 2400 or less. The viscosity average degree of polymerization P can be measured in accordance with JIS K6726 (1994). That is, the ethylene-vinyl alcohol copolymer (A) can be saponified to a degree of saponification of 99.5 mol% or more and purified, and then the limiting viscosity [η] (L/g) measured in water at 30°C can be determined by The formula is calculated. P=([η]×10000/8.29) (1/0.62)

(其它單體單元) 乙烯-乙烯醇共聚物(A)只要在不損害本發明的效果之範圍，則亦可含有乙烯醇單元、乙烯單元及乙烯酯單元以外之單體單元。作為如此的單體，可舉出丙烯、正丁烯、異丁烯等之α-烯烴；丙烯酸及其鹽；丙烯酸酯；甲基丙烯酸及其鹽；甲基丙烯酸酯；丙烯醯胺；N-甲基丙烯醯胺、N-乙基丙烯醯胺、N,N-二甲基丙烯醯胺、二丙酮丙烯醯胺、丙烯醯胺丙磺酸及其鹽、丙烯醯胺丙基二甲基胺及其鹽或其四級鹽、N-羥甲基丙烯醯胺及其衍生物等之丙烯醯胺衍生物；甲基丙烯醯胺；N-甲基甲基丙烯醯胺、N-乙基甲基丙烯醯胺、甲基丙烯醯胺丙磺酸及其鹽、甲基丙烯醯胺丙基二甲基胺及其鹽或其四級鹽、N-羥甲基甲基丙烯醯胺及其衍生物等之甲基丙烯醯胺衍生物；甲基乙烯基醚、乙基乙烯基醚、正丙基乙烯基醚、異丙基乙烯基醚、正丁基乙烯基醚、異丁基乙烯基醚、第三丁基乙烯基醚、十二基乙烯基醚、硬脂基乙烯基醚等之乙烯基醚；丙烯腈、甲基丙烯腈等之腈；氯乙烯、氟乙烯等之鹵乙烯；偏二氯乙烯、偏二氟乙烯等之偏二鹵乙烯；乙酸烯丙酯、烯丙基氯等之烯丙基化合物；馬來酸、伊康酸、富馬酸等之不飽和二羧酸及其鹽或其酯；乙烯基三甲氧基矽烷等之乙烯基矽基化合物；乙酸異丙烯酯等。此等之單體之含有率係隨著所使用之目的或用途等而不同，但較佳為10莫耳%以下，更佳為小於5莫耳%，尤佳為小於1莫耳%，特佳為小於0.5莫耳%。(Other monomer units) The ethylene-vinyl alcohol copolymer (A) may contain monomer units other than vinyl alcohol units, ethylene units, and vinyl ester units as long as they are within a range that does not impair the effects of the present invention. Examples of such monomers include α-olefins such as propylene, n-butene, and isobutylene; acrylic acid and its salts; acrylate; methacrylic acid and its salts; methacrylate; acrylamide; N-methyl Acrylic amide, N-ethyl acrylamide, N,N-dimethyl acrylamide, diacetone acrylamide, acrylamide propanesulfonic acid and its salt, acrylamide propyl dimethyl amine and its Salt or its quaternary salt, acrylamide derivatives such as N-methylol acrylamide and its derivatives; methacrylamide; N-methyl methacrylamide, N-ethyl methacrylate Amide, methacrylamide propanesulfonic acid and its salt, methacrylamide propyldimethylamine and its salt or its quaternary salt, N-methylol methacrylamide and its derivatives, etc. The methacrylamide derivatives; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, the first Vinyl ethers such as tributyl vinyl ether, dodecyl vinyl ether and stearyl vinyl ether; nitrile such as acrylonitrile and methacrylonitrile; vinyl halide such as vinyl chloride and vinyl fluoride; vinylidene chloride Vinylidene halides such as ethylene and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid and their salts Or its esters; vinyl silyl compounds such as vinyl trimethoxysilane; isopropenyl acetate, etc. The content of these monomers varies with the purpose or purpose of use, but it is preferably less than 10 mol%, more preferably less than 5 mol%, and particularly preferably less than 1 mol%. Preferably, it is less than 0.5 mol%.

[乙烯-乙烯醇共聚物(A)之製造方法] 乙烯-乙烯醇共聚物(A)之合適的製造方法係包含以下步驟的乙烯-乙烯醇共聚物之製造方法：將乙烯與乙烯酯共聚合而得到乙烯-乙烯酯共聚物之聚合步驟；將前述乙烯-乙烯酯共聚物皂化，得到包含乙烯-乙烯醇共聚物與溶劑之固體塊之皂化步驟；將前述固體塊粉碎而得到濕粒子之粉碎步驟；從前述濕粒子，將前述溶劑之一部分予以機械地脫液而得到脫液粒子之脫液步驟；及藉由從前述脫液粒子，加熱前述溶劑之剩餘部分而去除，得到乾燥粒子之乾燥步驟；其中 前述脫液粒子含有40～65質量%的前述溶劑，且 前述脫液粒子中之通過孔徑5.6mm的篩之粒子的含有率為80質量%以上，通過孔徑1.0mm的篩之粒子的含有率小於2質量%。[Method for manufacturing ethylene-vinyl alcohol copolymer (A)] A suitable production method of ethylene-vinyl alcohol copolymer (A) is a production method of ethylene-vinyl alcohol copolymer comprising the following steps: a polymerization step of copolymerizing ethylene and vinyl ester to obtain an ethylene-vinyl ester copolymer; The saponification step of saponification of the ethylene-vinyl ester copolymer to obtain a solid block containing the ethylene-vinyl alcohol copolymer and a solvent; a pulverization step of pulverizing the solid block to obtain wet particles; from the wet particles, a part of the solvent is mechanically A step of deliquoring the ground to obtain deliquored particles; and a step of drying by heating the remaining part of the solvent from the deliquoring particles to obtain dry particles; wherein The aforementioned deliquoring particles contain 40-65% by mass of the aforementioned solvent, and The content rate of the particles passing through the sieve with a pore size of 5.6mm in the aforementioned deliquored particles is 80% by mass or more, and the content rate of the particles passing through the sieve with the pore size of 1.0mm is less than 2% by mass.

如上述製造方法，將皂化步驟後的固體塊粉碎後，進行脫液而得之脫液粒子重要的是包含特定比例的溶劑，且具有特定的粒度分布，藉由此等，於調製乙烯-乙烯醇共聚物(A)的水溶液之際，不形成粉塊，溶解速度變大。以下，詳細說明製造方法之各步驟。As in the above-mentioned manufacturing method, the deliquored particles obtained by pulverizing the solid mass after the saponification step and deliquoring are important to contain a specific ratio of solvent and have a specific particle size distribution. By this, the preparation of ethylene-ethylene In the case of an aqueous solution of the alcohol copolymer (A), no lumps are formed, and the dissolution rate increases. Hereinafter, each step of the manufacturing method will be described in detail.

(聚合步驟) 作為乙烯與乙烯酯的共聚合之方法，可舉出塊狀聚合法、溶液聚合法、懸浮聚合法、乳化聚合法等眾所周知之方法。其中，通常可採用無溶劑或在醇等之有機溶劑中聚合之塊狀聚合法或溶液聚合法，但較佳為溶液聚合法。作為上述醇，可舉出甲醇、乙醇等之低級醇，特佳為甲醇。於聚合操作時，可採用批式法、半批式法及連續法之任一聚合方式。作為聚合反應器，可舉出批式反應器、管型反應器、連續槽型反應器等。作為共聚合所使用的起始劑，可舉出2,2'-偶氮雙(異丁腈)、2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基-戊腈)、過氧化苯甲醯、正丙基過氧二碳酸酯等之偶氮系起始劑或過氧化物系起始劑等之眾所周知的起始劑。(Polymerization step) As a method of copolymerization of ethylene and vinyl ester, well-known methods, such as a block polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method, are mentioned. Among them, a bulk polymerization method or a solution polymerization method without solvent or polymerization in an organic solvent such as alcohol can be generally used, but a solution polymerization method is preferred. Examples of the above alcohol include lower alcohols such as methanol and ethanol, and methanol is particularly preferred. In the polymerization operation, any polymerization method of batch method, semi-batch method and continuous method can be adopted. Examples of the polymerization reactor include batch reactors, tubular reactors, continuous tank reactors, and the like. As the initiator used in the copolymerization, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylpentane Nitrile), 2,2'-azobis(2,4-dimethyl-valeronitrile), benzoyl peroxide, n-propyl peroxydicarbonate and other azo initiators or peroxides It is a well-known initiator such as the initiator.

聚合溫度係沒有特別的限定，但較佳為0～180℃左右，更佳為室溫～160℃，尤佳為30～150℃。在聚合時使用的溶劑之沸點以下進行聚合之際，可選擇減壓沸騰聚合、常壓非沸騰聚合之任一者。又，在聚合時使用的溶劑之沸點以上進行聚合之際，可選擇加壓非沸騰聚合、加壓沸騰聚合之任一者。The polymerization temperature is not particularly limited, but is preferably about 0 to 180°C, more preferably room temperature to 160°C, and particularly preferably 30 to 150°C. When the polymerization is performed below the boiling point of the solvent used in the polymerization, either vacuum boiling polymerization or normal pressure non-boiling polymerization can be selected. In addition, when performing polymerization at a boiling point or higher of the solvent used in the polymerization, either pressurized non-boiling polymerization or pressurized boiling polymerization can be selected.

聚合時的聚合反應器內之乙烯壓力較佳為0.01～0.9MPa，更佳為0.05～0.7MPa，尤佳為0.1～0.65MPa。聚合反應器出口的聚合率係沒有特別的限定，但較佳為10～90%，更佳為15～85%。The ethylene pressure in the polymerization reactor during the polymerization is preferably 0.01 to 0.9 MPa, more preferably 0.05 to 0.7 MPa, and particularly preferably 0.1 to 0.65 MPa. The polymerization rate at the outlet of the polymerization reactor is not particularly limited, but is preferably 10 to 90%, more preferably 15 to 85%.

於聚合步驟中，以調節所得之乙烯-乙烯酯共聚物之黏度平均聚合度等為目的，亦可使鏈轉移劑共存。作為鏈轉移劑，可舉出乙醛、丙醛、丁醛、苯甲醛等之醛；丙酮、甲基乙基酮、己酮、環己酮等之酮；2-羥基乙硫醇等之硫醇；硫代乙酸等之硫代羧酸；三氯乙烯、全氯乙烯等之鹵化烴等。其中，較宜使用醛及酮。鏈轉移劑之添加量係可按照所添加的鏈轉移劑之鏈轉移常數及目的之乙烯-乙烯酯共聚物之黏度平均聚合度而決定，但通常相對於100質量份的所使用之乙烯酯，為0.1～10質量份。In the polymerization step, for the purpose of adjusting the viscosity and average degree of polymerization of the obtained ethylene-vinyl ester copolymer, a chain transfer agent may also coexist. Examples of chain transfer agents include aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, and benzaldehyde; ketones such as acetone, methyl ethyl ketone, hexanone, and cyclohexanone; sulfur such as 2-hydroxyethanethiol Alcohol; thiocarboxylic acid such as thioacetic acid; halogenated hydrocarbon such as trichloroethylene and perchloroethylene. Among them, aldehydes and ketones are more suitable. The amount of chain transfer agent added can be determined according to the chain transfer constant of the added chain transfer agent and the viscosity average degree of polymerization of the intended ethylene-vinyl ester copolymer, but it is usually relative to 100 parts by mass of the vinyl ester used. It is 0.1-10 parts by mass.

(皂化步驟) 將聚合步驟所得之乙烯-乙烯酯共聚物，在有機溶劑中，於觸媒之存在下藉由醇解或水解反應而皂化。作為皂化步驟所用的觸媒，可舉出氫氧化鈉、氫氧化鉀、甲氧化鈉等之鹼性觸媒；或硫酸、鹽酸、對甲苯磺酸等之酸性觸媒。皂化步驟所用的有機溶劑係沒有特別的限定，可舉出甲醇、乙醇等之醇；乙酸甲酯、乙酸乙酯等之酯；丙酮、甲基乙基酮等之酮；苯、甲苯等之芳香族烴等。此等係可單獨1種或併用2種以上而使用。其中，使用甲醇或甲醇與乙酸甲酯之混合溶液作為溶劑，於鹼性觸媒的氫氧化鈉之存在下進行皂化反應者係簡便而較宜。相對於乙烯-乙烯酯共聚物中的乙烯酯單體單元，皂化觸媒的使用量係莫耳比較佳為0.001～0.5。該莫耳比更佳為0.002以上。另一方面，該莫耳比較佳為0.4以下，更佳為0.3以下。(Saponification step) The ethylene-vinyl ester copolymer obtained in the polymerization step is saponified by alcoholysis or hydrolysis in the presence of a catalyst in an organic solvent. Examples of the catalyst used in the saponification step include alkaline catalysts such as sodium hydroxide, potassium hydroxide, and sodium methoxide; or acidic catalysts such as sulfuric acid, hydrochloric acid, and p-toluenesulfonic acid. The organic solvent used in the saponification step is not particularly limited. Examples include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatics such as benzene and toluene. Group hydrocarbons and so on. These systems can be used individually by 1 type or in combination of 2 or more types. Among them, the use of methanol or a mixed solution of methanol and methyl acetate as a solvent, and the saponification reaction in the presence of sodium hydroxide as an alkaline catalyst is simple and suitable. Relative to the vinyl ester monomer unit in the ethylene-vinyl ester copolymer, the amount of the saponification catalyst used is preferably 0.001 to 0.5 in moles. The molar ratio is more preferably 0.002 or more. On the other hand, the molar ratio is preferably 0.4 or less, and more preferably 0.3 or less.

皂化步驟之合適實施態樣係如以下。首先，對於聚合步驟中所得之乙烯-乙烯酯共聚物溶液，添加如氫氧化鈉之皂化觸媒及混合。此時之溶劑較佳為甲醇。雖然混合當初為均勻的液體，但在皂化反應進行，皂化聚合物中的乙烯酯單元而轉換成乙烯醇單元時，在溶劑中的溶解度降低，聚合物係析出至溶液中。此時，溶液中包含因甲醇所致的醇解而生成的乙酸甲酯。隨著皂化反應進行，聚合物的析出量徐徐地增加而成為漿體狀，然後喪失流動性。因此，為了使皂化反應均勻地進行，重要的是充分地混合直到喪失流動性為止。Suitable implementation aspects of the saponification step are as follows. First, to the ethylene-vinyl ester copolymer solution obtained in the polymerization step, a saponification catalyst such as sodium hydroxide is added and mixed. The solvent at this time is preferably methanol. Although the mixing was originally a homogeneous liquid, when the saponification reaction progresses and the vinyl ester units in the saponified polymer are converted into vinyl alcohol units, the solubility in the solvent decreases, and the polymer system precipitates into the solution. At this time, the solution contains methyl acetate produced by alcoholysis caused by methanol. As the saponification reaction proceeds, the amount of polymer precipitated gradually increases to become a slurry, and then loses fluidity. Therefore, in order for the saponification reaction to proceed uniformly, it is important to mix well until the fluidity is lost.

混合乙烯-乙烯酯共聚物溶液與皂化觸媒之方法係沒有特別的限定，可採用靜態混合器、捏合機、攪拌翼等各式各樣的方法，但使用靜態混合器者係可連續地均勻混合而較宜。此時，於聚合槽所連接的配管中，將皂化觸媒添加至聚合步驟後的乙烯-乙烯酯共聚物溶液，然後使其通過靜態混合器而混合，得到糊。靜態混合器中的反應液之溫度通常為20～80℃。The method of mixing the ethylene-vinyl ester copolymer solution and the saponification catalyst is not particularly limited. Various methods such as static mixers, kneaders, stirring blades, etc. can be used, but those using static mixers can be continuously uniform It is better to mix. At this time, in the piping connected to the polymerization tank, the saponification catalyst is added to the ethylene-vinyl ester copolymer solution after the polymerization step, and then it is passed through a static mixer and mixed to obtain a paste. The temperature of the reaction liquid in the static mixer is usually 20 to 80°C.

使通過靜態混合器後的糊中之乙烯-乙烯酯共聚物進行皂化反應之方法係沒有特別的限定，但較佳為在移動的帶(belt)之上載置該糊，一邊使該帶在保持一定溫度的槽中移動，一邊使皂化反應進行之方法。帶上的糊係喪失流動性而成為固體狀態，更以固體狀態進行皂化反應。藉由此方法，可以固體狀態使其連續地進行皂化反應，得到包含乙烯-乙烯醇共聚物與溶劑之固體塊。皂化溫度較佳為20～60℃。皂化溫度過低時，反應速度降低。皂化溫度更佳為25℃以上，尤佳為30℃以上。另一方面，若皂化溫度過高，則大量的溶劑蒸發，所得之固體塊中的溶劑之含有率變低，所得之乙烯-乙烯醇共聚物的溶解性會變差。皂化溫度更佳為55℃以下，尤佳為50℃以下。皂化時間較佳為5分鐘以上2小時以下。皂化時間更佳為8分鐘以上，尤佳為10分鐘以上。又，皂化時間為1小時以下，更佳為45分鐘以下。The method of saponifying the ethylene-vinyl ester copolymer in the paste after passing through the static mixer is not particularly limited, but it is preferable to place the paste on a moving belt while keeping the belt A method of moving in a tank at a certain temperature while allowing the saponification reaction to proceed. The paste on the belt loses fluidity and becomes a solid state, and the saponification reaction proceeds in a solid state. By this method, the saponification reaction can be continuously performed in a solid state to obtain a solid block containing an ethylene-vinyl alcohol copolymer and a solvent. The saponification temperature is preferably 20-60°C. When the saponification temperature is too low, the reaction rate decreases. The saponification temperature is more preferably 25°C or higher, particularly preferably 30°C or higher. On the other hand, if the saponification temperature is too high, a large amount of solvent will evaporate, the solvent content in the obtained solid block will become low, and the solubility of the obtained ethylene-vinyl alcohol copolymer will become poor. The saponification temperature is more preferably 55°C or less, and particularly preferably 50°C or less. The saponification time is preferably 5 minutes or more and 2 hours or less. The saponification time is more preferably 8 minutes or more, particularly preferably 10 minutes or more. In addition, the saponification time is 1 hour or less, more preferably 45 minutes or less.

(粉碎步驟) 藉由將皂化步驟所得之固體塊予以粉碎，得到含有溶劑的濕粒子。此時所用的粉碎機只要能調整粉碎機的旋轉數等，形成後述的粒度分布者，則沒有特別的限定，可使用眾所周知之粉碎機、破碎機。於經過皂化步驟所得之乙烯-乙烯醇共聚物的力學特性上，較佳為切碎機、鍘刀式切斷機、往復切刀式、一軸、二軸、三軸剪切破碎機等之切斷型破碎機。粉碎時與固體塊接觸的破碎刀之洛氏硬度(HRC)較佳為40～70。該硬度更佳為45以上。另一方面，該硬度更佳為65以下。又，破碎刀之旋轉數較佳為200～550rpm。該旋轉數更佳為225rpm以上，尤佳為250rpm以上。另一方面，該旋轉數更佳為500rpm以下，尤佳為450rpm以下。(Crushing step) The solid mass obtained in the saponification step is crushed to obtain wet particles containing a solvent. The pulverizer used at this time is not particularly limited as long as it can adjust the number of revolutions of the pulverizer and the like to form the particle size distribution described later, and well-known pulverizers and crushers can be used. In terms of the mechanical properties of the ethylene-vinyl alcohol copolymer obtained through the saponification step, it is preferably cut by a shredder, a guillotine cutter, a reciprocating cutter, a one-shaft, two-shaft, three-shaft shearing crusher, etc. Type crusher. The Rockwell hardness (HRC) of the crushing knife in contact with the solid block during pulverization is preferably 40-70. The hardness is more preferably 45 or more. On the other hand, the hardness is more preferably 65 or less. In addition, the rotation speed of the crushing knife is preferably 200 to 550 rpm. The number of rotations is more preferably 225 rpm or more, particularly preferably 250 rpm or more. On the other hand, the number of rotations is more preferably 500 rpm or less, and particularly preferably 450 rpm or less.

以往，於皂化步驟所得之固體塊的粉碎中，一般使用具備洛氏硬度小於40的破碎刀，以超過550rpm的旋轉數所運轉之粉碎機。由於所使用之破碎刀的洛氏硬度低，破碎刀之磨耗係容易進行，以經磨耗的破碎刀進行切斷者係容易發生粉碎不均。又，以高旋轉數將固體塊粉碎時，因粉碎的衝擊而固體塊在破碎機投入口中會大幅上下振動，會發生粉碎時的斷裂不均。根據如此之情事，以往難以安定地得到具有特定粒度分布之粒子。另一方面，破碎刀的洛氏硬度超過70時為高硬度，但另一方面由於韌性降低，在粉碎時會發生破碎刀的微小碎屑，因此有發生粉碎不均之傾向。又，粉碎機的旋轉數小於200rpm時，有粉碎效率降低之傾向。In the past, in the pulverization of the solid mass obtained in the saponification step, a pulverizer with a Rockwell hardness of less than 40 and a pulverizer operated at a rotation speed exceeding 550 rpm was generally used. Due to the low Rockwell hardness of the crushing knife used, the abrasion of the crushing knife is easy to proceed, and the cutting with a worn crushing knife is prone to uneven crushing. In addition, when the solid block is crushed with a high number of rotations, the solid block vibrates greatly up and down in the crusher inlet due to the impact of crushing, and uneven fracture during crushing may occur. Based on such circumstances, it has been difficult to stably obtain particles with a specific particle size distribution in the past. On the other hand, when the Rockwell hardness of the crushing blade exceeds 70, the hardness is high, but on the other hand, due to the decrease in toughness, fine chips of the crushing blade will be generated during crushing, so there is a tendency for uneven crushing. In addition, when the rotation speed of the pulverizer is less than 200 rpm, the pulverization efficiency tends to decrease.

(洗淨步驟) 於粉碎步驟之後，按照需要，以去除乙酸鈉等雜質為目的，可增加洗淨步驟而將濕粒子洗淨。作為洗淨液，可舉出甲醇、乙醇等之低級醇、乙酸甲酯等之低級脂肪酸酯及彼等之混合物等。洗淨步驟之條件係沒有特別的限定，但較佳為在20℃～洗淨液之沸點的溫度下，洗淨30分鐘～10小時左右。(Washing step) After the pulverization step, as needed, for the purpose of removing impurities such as sodium acetate, a washing step can be added to wash the wet particles. Examples of the cleaning solution include lower alcohols such as methanol and ethanol, lower fatty acid esters such as methyl acetate, and mixtures thereof. The condition of the washing step is not particularly limited, but it is preferably washing at a temperature of 20°C to the boiling point of the washing liquid for about 30 minutes to 10 hours.

(脫液步驟) 於粉碎步驟後，視情況於洗淨步驟後，從前述濕粒子中，藉由機械地脫液前述溶劑之一部分而得到脫液粒子。此時所用的脫液機較佳為離心脫液機。作為離心脫液機，較佳為連續的離心脫液為可能者，例如可舉出自動排出型離心脫液機、螺旋排出型離心脫液機、振動排出型離心脫液機、推出板型離心脫液機等。以往，於粉碎粒子之脫液中使用壓榨脫液機。然而，為了使所得之脫液粒子的溶劑含有率成為上述特定之範圍，必須增強壓榨強度，結果發生脫液粒子的變形或破壞，粒度分布脫離後述之範圍。即，於以往之方法中，難以同時達成後述的脫液粒子之粒度分布及溶劑含液率之值。於脫液步驟中，藉由使用上述的離心脫液機，可容易得到具有後述的粒度分布及溶劑含有率之脫液粒子。(Deliquoring step) After the pulverization step, and optionally, after the washing step, deliquoring particles are obtained by mechanically deliquoring a part of the solvent from the wet particles. The deliquid machine used at this time is preferably a centrifugal deliquid machine. As the centrifugal deliquoring machine, it is preferable that continuous centrifugal deliquoring is possible. For example, an automatic discharge type centrifugal deliquor, a screw discharge type centrifugal deliquid machine, a vibration discharge type centrifugal deliquid machine, and a push-out plate type centrifuge are mentioned. Deliquor etc. In the past, a press deliquor was used for deliquoring crushed particles. However, in order to make the solvent content of the obtained deliquored particles into the above-mentioned specific range, it is necessary to increase the pressing strength. As a result, the deliquored particles are deformed or broken, and the particle size distribution deviates from the range described later. That is, in the conventional method, it is difficult to achieve both the particle size distribution of the deliquored particles and the value of the solvent liquid content described later. In the deliquoring step, by using the above-mentioned centrifugal deliquoring machine, deliquored particles having the particle size distribution and solvent content described later can be easily obtained.

此處所得之脫液粒子含有40～65質量%的溶劑者係重要。溶劑之含有率小於40質量%時，過度乾燥的粒子係夾雜，在乾燥步驟後夾雜不易溶解的乙烯-乙烯醇共聚物，得不到能滿足上述式(I)之乙烯-乙烯醇共聚物(A)。溶劑之含有率較佳為42質量%以上，更佳為45質量%以上。另一方面，溶劑之含有率超過65質量%時，於粒子之表面與內部發生熱歷程差異，得不到能滿足上述式(I)之乙烯-乙烯醇共聚物(A)，乾燥所需要的能量係增加。溶劑之含有率較佳為62質量%以下，更佳為59質量%以下。溶劑之含有率係脫液粒子之平均值。相較於濕粒子中的溶劑之含有率，脫液粒子中的溶劑之含有率較佳為低3質量%以上，更佳為低5質量%以上，尤佳為低10質量%以上。It is important that the deliquored particles obtained here contain 40-65% by mass of the solvent. When the solvent content is less than 40% by mass, the excessively dried particles are mixed, and the ethylene-vinyl alcohol copolymer that is not easily soluble after the drying step cannot be obtained. The ethylene-vinyl alcohol copolymer (I) can not be obtained. A). The content of the solvent is preferably 42% by mass or more, more preferably 45% by mass or more. On the other hand, when the content of the solvent exceeds 65% by mass, a difference in thermal history occurs between the surface and the inside of the particles, and the ethylene-vinyl alcohol copolymer (A) that can satisfy the above formula (I) cannot be obtained, which is required for drying. Energy system increased. The content of the solvent is preferably 62% by mass or less, more preferably 59% by mass or less. The solvent content is the average value of the drained particles. Compared with the solvent content in the wet particles, the solvent content in the deliquoring particles is preferably lower by 3% by mass or more, more preferably by 5% by mass or more, and particularly preferably by 10% by mass or more.

又，前述脫液粒子中之通過孔徑5.6mm的篩之粒子的含有率為80質量%以上，通過孔徑1.0mm的篩之粒子之含有率小於2質量%者係重要。即，不含大量的粗大粒子，而且亦不含大量的微粒子者係重要。於本發明中，篩之孔徑係依據JIS Z 8801-1(2006年)的標稱孔徑。In addition, it is important that the content rate of particles passing through a sieve with a pore size of 5.6 mm in the deliquored particles is 80% by mass or more, and the content rate of particles passing through a sieve with a pore size of 1.0 mm is less than 2% by mass. That is, it is important that it does not contain a large amount of coarse particles and also does not contain a large amount of fine particles. In the present invention, the aperture of the sieve is based on the nominal aperture of JIS Z 8801-1 (2006).

前述脫液粒子中之通過孔徑5.6mm的篩之粒子的含有率為80質量%以上。脫液粒子含有大量的粗大粒子時，為了充分地乾燥到該粒子的中心為止，需要高溫或長時間的乾燥，乾燥所需要的能量增加。而且，由於施予高溫或長時間的乾燥，較小的粒子之結晶化係過度進行，在乾燥步驟後夾雜不易溶解的乙烯-乙烯醇共聚物粒子。又，由於粗大粒子之存在，發生乾燥機內的傳熱不均。由於如以上之情事，得不到能滿足上述式(I)之乙烯-乙烯醇共聚物(A)。通過孔徑5.6mm的篩之粒子的含有率較佳為82質量%以上，更佳為85質量%以上。另一方面，若考慮生產效率，則通過孔徑5.6mm的篩之粒子的含有率較佳為99質量%以下，更佳為98質量%以下。The content of particles passing through a sieve with an aperture of 5.6 mm in the aforementioned deliquored particles is 80% by mass or more. When the deliquored particles contain a large number of coarse particles, in order to sufficiently dry to the center of the particle, drying at a high temperature or a long time is required, and the energy required for drying increases. In addition, due to high temperature or long-term drying, the crystallization of the smaller particles proceeds excessively, and the ethylene-vinyl alcohol copolymer particles that are not easily soluble are included after the drying step. In addition, due to the presence of coarse particles, uneven heat transfer in the dryer occurs. Due to the above circumstances, the ethylene-vinyl alcohol copolymer (A) that satisfies the above formula (I) cannot be obtained. The content of particles passing through a sieve having an aperture of 5.6 mm is preferably 82% by mass or more, and more preferably 85% by mass or more. On the other hand, in consideration of production efficiency, the content of particles passing through a sieve with an aperture of 5.6 mm is preferably 99% by mass or less, and more preferably 98% by mass or less.

前述脫液粒子中之通過孔徑1.0mm的篩之粒子的含有率小於2質量%。脫液粒子含有大量的微粒子時，在其後因施予乾燥，而該微粒子的結晶化係過度進行，在乾燥步驟後多夾雜不易溶解的乙烯-乙烯醇共聚物粒子。又，微粒子滯留於乾燥機之底部，過量地受熱而結晶化度變過高，依然夾雜溶解性降低的乙烯-乙烯醇共聚物粒子。由於此等之情事，得不到能滿足上述式(I)之乙烯-乙烯醇共聚物(A)。通過孔徑1.0mm的篩之粒子的含有率較佳為1.9質量%以下，更佳為1.8質量%以下。另一方面，若考慮生產效率，則通過孔徑1.0mm的篩之粒子的含有率較佳為0.05質量%以上，更佳為0.1質量%以上。The content of particles passing through a sieve with an aperture of 1.0 mm among the aforementioned deliquored particles is less than 2% by mass. When the deliquored particles contain a large amount of fine particles, the crystallization system of the fine particles is excessively advanced due to subsequent drying, and the ethylene-vinyl alcohol copolymer particles which are not easily soluble are often contained after the drying step. In addition, the fine particles stay at the bottom of the dryer, are excessively heated, and the degree of crystallinity becomes too high, and the ethylene-vinyl alcohol copolymer particles with reduced solubility are still mixed. Due to these circumstances, an ethylene-vinyl alcohol copolymer (A) that satisfies the above formula (I) cannot be obtained. The content of particles passing through a sieve with an aperture of 1.0 mm is preferably 1.9% by mass or less, and more preferably 1.8% by mass or less. On the other hand, in consideration of production efficiency, the content of particles passing through a sieve with an aperture of 1.0 mm is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more.

(乾燥步驟) 於脫液步驟後將前述脫液粒子供應至乾燥步驟，可得到乙烯-乙烯醇共聚物。具體而言，較佳為使用圓筒乾燥機之熱風乾燥，乾燥時的粒子之溫度較佳為80～120℃。若該溫度過低，則生產效率降低。該溫度更佳為90℃以上。另一方面，若該溫度過高，則發生結晶化過度進行的粒子，溶解性變差。該溫度更佳為110℃以下。又，乾燥時間較佳為2～10小時，更佳為3～8小時。由於使乾燥時之條件成為上述範圍，可簡便地製造能滿足式(I)之乙烯-乙烯醇共聚物。(Drying step) After the deliquoring step, the aforementioned deliquoring particles are supplied to the drying step to obtain an ethylene-vinyl alcohol copolymer. Specifically, hot air drying using a drum dryer is preferable, and the temperature of the particles during drying is preferably 80 to 120°C. If the temperature is too low, the production efficiency decreases. The temperature is more preferably 90°C or higher. On the other hand, if the temperature is too high, particles with excessively advanced crystallization will occur, and the solubility will deteriorate. The temperature is more preferably 110°C or lower. In addition, the drying time is preferably 2 to 10 hours, more preferably 3 to 8 hours. Since the conditions during drying fall within the above-mentioned range, an ethylene-vinyl alcohol copolymer satisfying formula (I) can be easily produced.

(追加粉碎步驟) 於乾燥步驟後，為了更減小粒徑，較佳為設置追加粉碎步驟。藉此，可成為在水中的溶解速度大之粒子。追加粉碎步驟所使用的粉碎機係可使用與前述粉碎步驟所用者同樣的粉碎機。(Add crush step) After the drying step, in order to further reduce the particle size, an additional crushing step is preferably provided. This can become particles with a high dissolution rate in water. The crusher system used in the additional crushing step can use the same crusher as that used in the foregoing crushing step.

追加粉碎步驟所得之乙烯-乙烯醇共聚物(A)的粒子係通過孔徑2.5mm的篩之粒子的含有率較佳為80質量%以上。通過孔徑2.5mm的篩之粒子小於80質量%時，於使乙烯-乙烯醇共聚物(A)的粒子溶解於水中而調製水溶液時，溶解速度變低，需要高溫且長時間的加熱。通過孔徑2.5mm的篩之粒子的含有率更佳為83質量%以上，尤佳為85質量%以上。再者，乙烯-乙烯醇共聚物(A)的粒子係通過孔徑1.0mm的篩之粒子的含有率較佳為80質量%以上。藉此，在水中的溶解速度更升高。通過孔徑1.0mm的篩之粒子的含有率更佳為83質量%以上，尤佳為85質量%以上。The content of the particles of the ethylene-vinyl alcohol copolymer (A) obtained by the additional pulverizing step is preferably 80% by mass or more. When the particles passing through a sieve with a hole diameter of 2.5 mm are less than 80% by mass, when the particles of the ethylene-vinyl alcohol copolymer (A) are dissolved in water to prepare an aqueous solution, the dissolution rate becomes low, and high temperature and long-term heating are required. The content of particles passing through a sieve with an aperture of 2.5 mm is more preferably 83% by mass or more, and particularly preferably 85% by mass or more. Furthermore, the content of the particles of the ethylene-vinyl alcohol copolymer (A) passing through a sieve with an aperture of 1.0 mm is preferably 80% by mass or more. As a result, the dissolution rate in water is further increased. The content of particles passing through a sieve with an aperture of 1.0 mm is more preferably 83% by mass or more, and particularly preferably 85% by mass or more.

另一方面，追加粉碎步驟所得之乙烯-乙烯醇共聚物(A)的粒子係通過孔徑0.15mm的篩之粒子的含有率較佳為20質量%以下。通過孔徑0.15mm的篩之粒子的含有率超過20質量%時，在包含乙烯-乙烯醇共聚物(A)的水溶液中有容易發生粉塊之傾向。通過孔徑0.15mm的篩之粒子的含有率更佳為17質量%以下，尤佳為15質量%以下。On the other hand, the content of the particles of the ethylene-vinyl alcohol copolymer (A) obtained by the additional pulverization step is preferably 20% by mass or less. When the content of particles passing through a sieve with a pore size of 0.15 mm exceeds 20% by mass, agglomeration tends to be easily generated in the aqueous solution containing the ethylene-vinyl alcohol copolymer (A). The content of particles passing through a sieve with an aperture of 0.15 mm is more preferably 17% by mass or less, and particularly preferably 15% by mass or less.

[羧酸的金屬鹽(B)] 本發明之塗覆液係特徵為包含羧酸的鹼金屬鹽(B)。相對於100質量份的乙烯-乙烯醇系聚合物(A)，羧酸的鹼金屬鹽(B)之含有比例係以鹼金屬的質量換算為0.001～1質量份，較佳為0.01～0.9質量份，更佳為0.02～0.8質量份。含量超過1質量份時，塗覆紙的阻隔性、耐水性降低。此理由雖然未明，但推斷若羧酸的鹼金屬鹽(B)過剩地存在，則乙烯-乙烯醇共聚物(A)的水溶性降低，導致不溶物的增加或所生成的粉塊之溶解不良。另一方面，含量小於0.001質量份者係乙烯-乙烯醇共聚物(A)之製法上困難，為了達成而需要過剩的洗淨作業等，因此導致製造成本之增加。[Metal Salt of Carboxylic Acid (B)] The coating liquid system of the present invention is characterized by containing an alkali metal salt (B) of carboxylic acid. The content ratio of the alkali metal salt of carboxylic acid (B) relative to 100 parts by mass of the ethylene-vinyl alcohol polymer (A) is 0.001 to 1 part by mass, preferably 0.01 to 0.9 part by mass in terms of the mass of alkali metal Parts, more preferably 0.02 to 0.8 parts by mass. When the content exceeds 1 part by mass, the barrier properties and water resistance of the coated paper decrease. Although the reason for this is not clear, it is inferred that if the alkali metal salt of carboxylic acid (B) is present in excess, the water solubility of the ethylene-vinyl alcohol copolymer (A) will decrease, resulting in an increase in insoluble matter or poor dissolution of the resulting powder. . On the other hand, those with a content of less than 0.001 parts by mass are difficult in the production method of the ethylene-vinyl alcohol copolymer (A), and excessive cleaning operations and the like are required in order to achieve this, which leads to an increase in the production cost.

於本發明中，羧酸的鹼金屬鹽(B)之含量(鹼金屬的質量換算)係可在白金坩堝上使乾固的塗覆液灰化後，藉由ICP發光分析測定所得之灰分，從所得之鹼金屬離子量求出。In the present invention, the content of alkali metal salt of carboxylic acid (B) (calculated by mass of alkali metal) can be determined by ICP emission analysis after ashing the dry coating solution on a platinum crucible. It is calculated from the obtained alkali metal ion amount.

於本發明中，羧酸的鹼金屬鹽(B)係沒有特別的限制。例如，可舉出乙酸鈉、乙酸鉀、丙酸鈉、丙酸鉀、甘油酸鈉、甘油酸鉀、蘋果酸鈉、蘋果酸鉀、檸檬酸鈉、檸檬酸鉀、乳酸鈉、乳酸鉀、酒石酸鈉、酒石酸鉀、水楊酸鈉、水楊酸鉀、丙二酸鈉、丙二酸鉀、琥珀酸鈉、琥珀酸鉀、馬來酸鈉、馬來酸鉀、鄰苯二甲酸鈉、鄰苯二甲酸鉀、草酸鈉、草酸鉀、戊二酸鈉、戊二酸鉀、松脂酸鈉、松脂酸鉀、山梨酸鈉、山梨酸鉀、2,4,6-辛三烯-1-羧酸鈉、2,4,6-辛三烯-1-羧酸鉀、油硬脂酸鈉、油硬脂酸鉀、2,4,6,8-癸四烯-1-羧酸鈉、2,4,6,8-癸四烯-1-羧酸鉀、視黃酸鈉、視黃酸鉀等。In the present invention, the alkali metal salt (B) of carboxylic acid is not particularly limited. For example, sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium glycerate, potassium glycerate, sodium malate, potassium malate, sodium citrate, potassium citrate, sodium lactate, potassium lactate, sodium tartrate , Potassium tartrate, sodium salicylate, potassium salicylate, sodium malonate, potassium malonate, sodium succinate, potassium succinate, sodium maleate, potassium maleate, sodium phthalate, phthalate Potassium formate, sodium oxalate, potassium oxalate, sodium glutarate, potassium glutarate, sodium rosinate, potassium rosinate, sodium sorbate, potassium sorbate, sodium 2,4,6-octatriene-1-carboxylate , Potassium 2,4,6-octatriene-1-carboxylate, sodium oleostearate, potassium oleyl stearate, sodium 2,4,6,8-decatetraene-1-carboxylate, 2,4 , Potassium 6,8-decatetraene-1-carboxylate, sodium retinoate, potassium retinoate, etc.

於本發明中，使塗覆液含有特定量之羧酸的鹼金屬鹽(B)之方法係沒有特別的限制。例如，可舉出(1)將乙烯-乙烯醇共聚物、羧酸的鹼金屬鹽一起溶解於水中之方法，(2)於將乙烯-乙烯酯共聚物在溶劑中皂化之際，使用含有鹼金屬作為皂化觸媒之鹼性物質，將所得之摻合有羧酸的鹼金屬鹽之乙烯-乙烯醇共聚物溶解於水中之方法，(3)以抑制聚合步驟所使用的乙酸乙烯酯等之原料乙烯酯單體的醇解為目的而添加的羧酸係在皂化步驟被中和，將所得之摻合有羧酸的鹼金屬鹽之乙烯-乙烯醇共聚物溶解於水中之方法，(4)作為為了使自由基聚合停止而添加的抑制劑，使用具有共軛雙鍵的羧酸時，該羧酸係在皂化步驟中被中和，將所得之摻合有羧酸的鹼金屬鹽之乙烯-乙烯醇共聚物溶解於水中之方法等。In the present invention, the method for making the coating liquid contain a specific amount of the alkali metal salt (B) of carboxylic acid is not particularly limited. For example, (1) a method of dissolving an ethylene-vinyl alcohol copolymer and an alkali metal salt of a carboxylic acid in water together, (2) when saponifying an ethylene-vinyl ester copolymer in a solvent, using an alkali A method of dissolving the resulting ethylene-vinyl alcohol copolymer blended with an alkali metal salt of a carboxylic acid in water as an alkaline substance for the saponification catalyst; (3) to inhibit the effect of vinyl acetate used in the polymerization step, etc. The carboxylic acid system added for the purpose of alcoholysis of the raw material vinyl ester monomer is neutralized in the saponification step, and the resulting ethylene-vinyl alcohol copolymer blended with the alkali metal salt of the carboxylic acid is dissolved in water, (4 ) As an inhibitor added to stop radical polymerization, when a carboxylic acid having a conjugated double bond is used, the carboxylic acid is neutralized in the saponification step, and the obtained alkali metal salt doped with carboxylic acid Methods for dissolving ethylene-vinyl alcohol copolymer in water, etc.

本發明之紙用塗覆液之製造方法係沒有特別的限定。可藉由使滿足前述式(I)之乙烯-乙烯醇共聚物(A)的粒子溶解於水中，而得到本發明之紙用塗覆液。作為合適的製造方法，可舉出使滿足前述式(I)之包含羧酸的鹼金屬鹽(B)的乙烯-乙烯醇共聚物(A)的粒子溶解於水中之方法。又，作為其它合適的製造方法，可舉出使滿足前述式(I)之乙烯-乙烯醇共聚物(A)的粒子與羧酸的鹼金屬鹽(B)溶解於水中之方法。The manufacturing method of the coating liquid for paper of this invention is not specifically limited. The coating liquid for paper of the present invention can be obtained by dissolving particles of the ethylene-vinyl alcohol copolymer (A) satisfying the aforementioned formula (I) in water. As a suitable production method, a method of dissolving particles of an ethylene-vinyl alcohol copolymer (A) containing an alkali metal salt of carboxylic acid (B) satisfying the aforementioned formula (I) in water. In addition, as another suitable production method, a method of dissolving the particles of the ethylene-vinyl alcohol copolymer (A) satisfying the aforementioned formula (I) and the alkali metal salt of carboxylic acid (B) in water can be cited.

＜塗覆紙之製造＞ 於本發明之紙用塗覆液中，視需要可添加乙二醛、尿素樹脂、三聚氰胺樹脂、多價金屬鹽、水溶性聚醯胺樹脂等之耐水化劑；二醇類、甘油等之可塑劑；氨、苛性鈉、碳酸鈉、磷酸等之pH調節劑；消泡劑；脫模劑；界面活性劑；顏料等之著色劑等各種的添加劑。再者，於本發明之紙用塗覆液中，在不妨礙本發明的效果之範圍內，可併用無改質PVA、羧基改質PVA、磺酸基改質PVA、丙烯醯胺改質PVA、陽離子基改質PVA、長鏈烷基改質PVA等之各種的改質PVA；酪蛋白、生澱粉(小麥、玉米、米、馬鈴薯、甘薯、樹薯、西谷椰子)、生澱粉分解產物(糊精等)、澱粉衍生物(氧化澱粉、醚化澱粉、酯化澱粉、陽離子化澱粉等)、海藻多糖類(海藻酸鈉、鹿角菜膠、洋菜(瓊脂糖、瓊脂膠)、叉紅藻膠等)、水溶性纖維素衍生物(羧基烷基纖維素、烷基纖維素、羥基烷基纖維素等)等之水溶性高分子；苯乙烯-丁二烯共聚物乳膠、聚丙烯酸酯乳液、乙酸乙烯酯-乙烯共聚物乳液、乙酸乙烯酯-丙烯酸酯共聚物乳液等之合成樹脂乳液。＜Manufacture of coated paper＞ In the coating liquid for paper of the present invention, water-resistant agents such as glyoxal, urea resin, melamine resin, polyvalent metal salt, water-soluble polyamide resin, etc. can be added as needed; plastics such as glycols, glycerin, etc. Agents; pH regulators such as ammonia, caustic soda, sodium carbonate, phosphoric acid, etc.; defoamers; mold release agents; surfactants; various additives such as coloring agents for pigments. Furthermore, in the coating liquid for paper of the present invention, unmodified PVA, carboxyl-modified PVA, sulfonic acid-modified PVA, and acrylamide-modified PVA can be used together within the range that does not hinder the effects of the present invention. , Cationic modified PVA, long-chain alkyl modified PVA, etc. various modified PVA; casein, raw starch (wheat, corn, rice, potato, sweet potato, cassava, sago palm), raw starch decomposition products ( Dextrin, etc.), starch derivatives (oxidized starch, etherified starch, esterified starch, cationized starch, etc.), seaweed polysaccharides (sodium alginate, carrageenan, agar (agarose, agar gum), cross red Alginate, etc.), water-soluble cellulose derivatives (carboxyalkyl cellulose, alkyl cellulose, hydroxyalkyl cellulose, etc.) and other water-soluble polymers; styrene-butadiene copolymer latex, polyacrylate Synthetic resin emulsions such as emulsions, vinyl acetate-ethylene copolymer emulsions, vinyl acetate-acrylate copolymer emulsions.

本發明中的塗覆液中之乙烯-乙烯醇共聚物(A)之濃度係按照塗覆量(因塗布所發生的紙之乾燥質量的增加)、塗布所使用的裝置、操作條件等而任意地選擇，但較佳為1.0～10質量%，更佳為2.0～9.0質量%。而且，塗覆量係可按照塗布對象的紙之性質形狀而任意選擇，但通常紙之每單面較佳為0.3～3.0g/m2 左右。又，塗覆液之黏度係在40℃下較佳為0.001～1Pa・s左右。The concentration of the ethylene-vinyl alcohol copolymer (A) in the coating solution of the present invention is arbitrarily based on the coating amount (the increase in the dry mass of the paper due to coating), the equipment used for coating, operating conditions, etc. However, it is preferably 1.0-10% by mass, and more preferably 2.0-9.0% by mass. In addition, the coating amount can be arbitrarily selected according to the nature and shape of the paper to be coated, but generally, it is preferably about 0.3 to 3.0 g/m 2 per single side of the paper. In addition, the viscosity of the coating liquid is preferably about 0.001 to 1 Pa·s at 40°C.

作為將水溶液或水性分散液的本發明之塗覆液塗布於紙上之方法，通常使用眾所周知之方法，例如使用施膠壓機、水平輥塗佈機、西姆施膠機(sym-sizer)、棒塗機等之裝置，塗布於紙之單面或兩面之方法，可使用使塗覆液含浸至紙之方法。又，經塗布的紙之乾燥係可藉由眾所周知之方法，例如熱風、紅外線、加熱筒或組合此等之方法而進行，經乾燥的塗覆紙係可藉由調濕及壓延機處理，而進一步提高阻隔性。作為壓延機處理條件，輥溫度較佳為常溫～100℃，輥線壓較佳為20～300kg/cm。As a method for coating the coating liquid of the present invention in an aqueous solution or aqueous dispersion on paper, a well-known method is generally used, such as a sizing press, a horizontal roll coater, a sym-sizer, For devices such as bar coaters, the method of coating one or both sides of paper can be a method of impregnating the paper with the coating liquid. In addition, the drying of the coated paper can be carried out by well-known methods, such as hot air, infrared rays, heating cylinders, or a combination of these methods, and the dried coated paper can be processed by humidity control and calendering. Further improve barrier properties. As the processing conditions of the calender, the roll temperature is preferably from room temperature to 100°C, and the roll pressure is preferably from 20 to 300 kg/cm.

作為使用本發明之塗覆液的塗覆紙，並沒有特別的限定，但較佳為剝離紙。剝離紙係基材(紙)之上具有將前述紙用塗覆液塗布而形成的填隙層(阻隔層)。即，於將本發明之塗覆液塗布於紙而形成的填隙層之上形成剝離層而成的剝離紙，係合適的實施態樣。作為所用的紙，並沒有特別的限制，可舉出白紙板(manila board)、白紙板(White chipboard)、襯紙等之板紙；一般上等紙、中等紙、凹版用紙等之印刷紙等。又，剝離紙進一步具有形成於填隙層之上的剝離層。作為剝離層，並沒有特別的限定，但較佳為聚矽氧樹脂。聚矽氧樹脂係沒有特別的限定，可使用眾所周知者。作為如此的聚矽氧樹脂，可舉出溶劑型聚矽氧、無溶劑型聚矽氧、乳液型聚矽氧。The coated paper using the coating liquid of the present invention is not particularly limited, but is preferably a release paper. The release paper base material (paper) has a gap-filling layer (barrier layer) formed by coating the aforementioned paper coating liquid. That is, a release paper obtained by forming a release layer on a gap-filling layer formed by applying the coating liquid of the present invention to paper is a suitable embodiment. The paper used is not particularly limited. Examples include board paper such as manila board, white chipboard, and interleaving paper; printing paper such as general fine paper, medium paper, and intaglio paper. In addition, the release paper further has a release layer formed on the gap-filling layer. The release layer is not particularly limited, but is preferably silicone resin. The silicone resin system is not particularly limited, and well-known ones can be used. Examples of such silicone resins include solvent-based silicones, solvent-free silicones, and emulsion-based silicones.

於本發明之剝離紙的剝離層中，除了上述以外，亦可適宜地摻合一般製紙用途所使用的顏料、螢光增白劑、螢光增白劑之被染附物質、消泡劑、脫模劑、著色劑、保水劑等之通常使用的各種藥品。In the release layer of the release paper of the present invention, in addition to the above, pigments, fluorescent brighteners, dyed substances of fluorescent brighteners, defoamers, Various commonly used chemicals such as mold release agents, colorants, and water-retaining agents.

剝離層用塗覆液之塗布係只要以一般的塗覆紙用途設備進行就夠了，例如可藉由設有刮刀塗布機、氣刀塗布機、轉移輥塗布機、水平輥施膠壓機、二輥施膠壓機、棒金屬化施膠壓機塗布機、簾式塗布機等之塗布裝置的機上塗布機或機外塗布機，在原紙上以一層或分成多層來塗布塗覆液。其中，從適合機上塗布機之觀點來看，較佳為使用水平輥施膠壓機、二輥施膠壓機、棒金屬化施膠壓機塗布機。又，作為乾燥部之乾燥方法，例如可適宜採用熱旋轉滾筒、熱風加熱、氣體加熱器加熱、紅外線加熱器加熱等之各種加熱乾燥方式。剝離層之塗覆量係乾燥質量較佳為0.3～1.8g/m2 ，更佳為0.5～1.5g/m2 。The coating of the coating liquid for the release layer is sufficient as long as the general equipment for coating paper is used. For example, it can be equipped with a knife coater, an air knife coater, a transfer roll coater, a horizontal roll sizing press, Two-roll sizing press, bar metallized sizing press coater, curtain coater and other coating devices such as on-machine or off-machine coater coat the coating liquid in one layer or multiple layers on the base paper. Among them, it is preferable to use a horizontal roll sizing press, a two-roll sizing press, and a bar metalizing sizing press coater from the viewpoint of being suitable for an on-machine coating machine. In addition, as the drying method of the drying section, various heating and drying methods such as thermal rotating drum, hot air heating, gas heater heating, infrared heater heating, etc. can be suitably used. The coating amount of the release layer is preferably 0.3 to 1.8 g/m 2 in dry mass, more preferably 0.5 to 1.5 g/m 2 .

本發明之剝離紙之製造方法係沒有特別的限定。可藉由將本發明之塗覆液塗布於紙上而形成填隙層，於該填隙層之上塗布剝離層用塗覆液而製造。The manufacturing method of the release paper of this invention is not specifically limited. It can be manufactured by coating the coating liquid of the present invention on paper to form a gap-filling layer, and coating the gap-filling layer with the coating fluid for a release layer.

作為後加工步驟所使用的水分散性清漆，例如可舉出苯乙烯-丁二烯共聚物乳膠、甲基丙烯酸甲酯-丁二烯共聚物乳膠、苯乙烯-甲基丙烯酸甲酯-丁二烯共聚物乳膠等之共軛二烯系乳膠；丙烯酸酯及/或甲基丙烯酸酯之聚合物乳膠或共聚物乳膠等之丙烯酸系乳膠；乙烯-乙酸乙烯酯聚合物乳膠等之乙烯系乳膠等，可從此等之中適宜選擇1種或2種以上而使用。As the water-dispersible varnish used in the post-processing step, for example, styrene-butadiene copolymer latex, methyl methacrylate-butadiene copolymer latex, styrene-methyl methacrylate-butadiene Conjugated diene latex such as olefin copolymer latex; acrylic latex such as acrylate and/or methacrylate polymer latex or copolymer latex; vinyl latex such as ethylene-vinyl acetate polymer latex, etc. One or two or more of these can be appropriately selected and used.

作為塗布有本發明之紙用塗覆液的塗覆紙，依據JIS P 8117(2009年)，使用王研式滑度透氣度試驗機所測定的透過度較佳為20000秒以上，更佳為23000秒以上，尤佳為25000秒以上。藉此，可減低構成紙的紙漿纖維間之空隙而提高阻隔性。而且，於紙基材上塗布本發明之塗覆液而形成的具有填隙層的剝離紙原紙，由於對於有機溶劑等具有優異的阻隔性。結果，於填隙層之上塗布剝離層時，可提高聚矽氧樹脂的表面良率。As the coated paper coated with the coating liquid for paper of the present invention, in accordance with JIS P 8117 (2009), the transmittance measured using the Wangyan type slip air permeability tester is preferably 20,000 seconds or more, more preferably 23000 seconds or more, more preferably 25000 seconds or more. Thereby, the voids between the pulp fibers constituting the paper can be reduced and the barrier properties can be improved. In addition, the release paper base paper with the interstitial layer formed by coating the coating liquid of the present invention on a paper substrate has excellent barrier properties against organic solvents and the like. As a result, when the release layer is coated on the interstitial layer, the surface yield of the silicone resin can be improved.

又，作為本發明之紙用塗覆液，依據JIS P 8140(1998年)，以塗覆紙與水的接觸時間為60秒時之柯布(Cobb)法所測定的吸水度較佳為70g/m2 以下，更佳為50g/m2 以下，尤佳為45g/m2 以下。藉此，剝離紙中的填隙層之耐水性變良好，可在後加工步驟使用水分散性清漆。In addition, as the coating liquid for paper of the present invention, according to JIS P 8140 (1998), the water absorption measured by the Cobb method when the contact time of the coated paper with water is 60 seconds is preferably 70 g /m 2 or less, more preferably 50 g/m 2 or less, and particularly preferably 45 g/m 2 or less. Thereby, the water resistance of the interstitial layer in the release paper becomes better, and the water-dispersible varnish can be used in the post-processing step.

本發明係只要達成本發明之效果，則在本發明之技術範圍內，包含組合各種上述之構成的組合之態樣。As long as the present invention achieves the effects of the present invention, it is within the technical scope of the present invention to include various combinations of the aforementioned configurations.

塗布有本發明之塗覆液的塗覆紙係耐水性優異，同時阻隔性亦優異。因此，該塗覆紙例如係適用於剝離紙等。再者，本發明之紙用塗覆液係藉由耐水性之改善，而抗黏連性亦優異，同時在後加工步驟中可使用水分散性清漆。 [實施例]The coated paper coated with the coating liquid of the present invention is excellent in water resistance and barrier properties. Therefore, the coated paper is suitable for release paper, for example. Furthermore, the coating liquid for paper of the present invention is improved in water resistance, and has excellent blocking resistance. At the same time, a water-dispersible varnish can be used in post-processing steps. [Example]

以下，舉出實施例來更具體地說明本發明，惟本發明完全不受此等之實施例所限定。Hereinafter, examples are given to explain the present invention more specifically, but the present invention is not limited by these examples at all.

[乙烯-乙烯醇共聚物(A)的乙烯單元之含有率] 由乙烯-乙烯醇共聚物的前驅物或再乙醯化物之乙烯-乙烯酯共聚物之1 H-NMR求出。即，使用正己烷與丙酮的混合溶液，進行3次以上的所得之乙烯-乙烯酯共聚物之再沈澱純化後，進行80℃下的減壓乾燥3日，製作分析用的乙烯-乙烯酯共聚物。將分析用的乙烯-乙烯酯共聚物溶解於DMSO-d6 中，在80℃測定1 H-NMR(500MHz)。使用源自乙烯酯的主鏈次甲基之波峰(4.7～5.2ppm)與源自乙烯、乙烯酯的主鏈亞甲基之波峰(0.8～1.6ppm)，算出乙烯單元之含有率。[The ethylene unit content of the ethylene-vinyl alcohol copolymer (A)] It was determined from 1 H-NMR of the ethylene-vinyl ester copolymer of the precursor of the ethylene-vinyl alcohol copolymer or the re-acetylated product. That is, after performing reprecipitation purification of the obtained ethylene-vinyl ester copolymer 3 times or more using a mixed solution of n-hexane and acetone, it was dried under reduced pressure at 80°C for 3 days to produce an ethylene-vinyl ester copolymer for analysis. Things. The ethylene-vinyl ester copolymer for analysis was dissolved in DMSO-d 6 and 1 H-NMR (500 MHz) was measured at 80°C. The peak (4.7-5.2 ppm) of the main chain methine derived from vinyl ester and the peak (0.8-1.6 ppm) of the main chain methylene derived from ethylene and vinyl ester were used to calculate the ethylene unit content.

[乙烯-乙烯醇共聚物(A)之黏度平均聚合度] 乙烯-乙烯醇共聚物(A)之黏度平均聚合度係藉由JIS K6726(1994年)中記載之方法求出。[Viscosity average degree of polymerization of ethylene-vinyl alcohol copolymer (A)] The viscosity average degree of polymerization of the ethylene-vinyl alcohol copolymer (A) is determined by the method described in JIS K6726 (1994).

[乙烯-乙烯醇共聚物(A)之皂化度] 乙烯-乙烯醇共聚物(A)之皂化度係藉由JIS K6726(1994年)中記載之方法求出。[Saponification degree of ethylene-vinyl alcohol copolymer (A)] The saponification degree of the ethylene-vinyl alcohol copolymer (A) is determined by the method described in JIS K6726 (1994).

[乙烯-乙烯醇共聚物(A)之羧酸的鹼金屬鹽含量測定] 乙烯-乙烯醇共聚物(A)之羧酸的鹼金屬鹽含量(鹼金屬的質量換算)係在將乙烯-乙烯醇共聚物(A)灰化後，使用Jarrell-Ash公司製ICP發光分析裝置「IRIS AP」，藉由測定所得之灰分中的鹼金屬量而求出。[Determination of alkali metal salt content of carboxylic acid in ethylene-vinyl alcohol copolymer (A)] The alkali metal salt content of the carboxylic acid of the ethylene-vinyl alcohol copolymer (A) (calculated by the mass of alkali metal) is based on ashing the ethylene-vinyl alcohol copolymer (A) and using the ICP emission analyzer manufactured by Jarrell-Ash "IRIS AP" is determined by measuring the amount of alkali metal in the ash obtained.

[乙烯-乙烯醇共聚物(A)之水中結晶化度] 將乙烯-乙烯醇共聚物(A)之試料靜置於各溫度(30℃、70℃)之H2 O-d2 中40分鐘後，於與靜置時的溫度相同的溫度下進行脈衝NMR測定。以下述式(III)，使用誤差最小平方法來擬合所得之緩和曲線的0～0.8ms之範圍。[Crystallinity of ethylene-vinyl alcohol copolymer (A) in water] After placing the sample of ethylene-vinyl alcohol copolymer (A) in H 2 Od 2 at various temperatures (30°C, 70°C) for 40 minutes, The pulse NMR measurement was performed at the same temperature as the temperature at the time of standing. According to the following formula (III), the error least square method is used to fit the range of 0-0.8 ms of the obtained relaxation curve.

Figure 02_image009
Figure 02_image009

[粉塊性] 於300ml可分離式燒瓶中置入150ml的蒸餾水，升溫到內溫成為70℃為止。升溫後，於150rpm之攪拌下添加6g的乙烯-乙烯醇共聚物，目視觀察添加後立即的乙烯-乙烯醇共聚物粒子之狀態，如以下地評價。 A：不成為粉塊。 B：成為粉塊，但藉由5分鐘的攪拌而消除粉塊。 C：成為粉塊，即使攪拌5分鐘也無法消除粉塊。[Pinkness] Put 150ml of distilled water in a 300ml separable flask, and raise the temperature until the internal temperature reaches 70°C. After the temperature was raised, 6 g of ethylene-vinyl alcohol copolymer was added under stirring at 150 rpm, and the state of the ethylene-vinyl alcohol copolymer particles immediately after the addition was visually observed, and the evaluation was as follows. A: It does not become a powder block. B: It becomes a lumps, but the lumps are eliminated by stirring for 5 minutes. C: The lumps are formed, and the lumps cannot be eliminated even after stirring for 5 minutes.

[溶解性] 於500ml可分離式燒瓶中置入288g的蒸餾水，升溫到內溫成為85℃為止。升溫後，於150rpm之攪拌下添加12g的乙烯-乙烯醇共聚物。於添加後經過30分鐘後的階段中，採集乙烯-乙烯醇共聚物水溶液。以No.5A的濾紙過濾所採集的水溶液，將其濾液在125℃乾燥3小時，求出水溶液中所溶解的乙烯-乙烯醇共聚物之質量A(g)。又，將12g的試料之乙烯-乙烯醇共聚物粒子在125℃乾燥3小時，求出其不揮發分量B(g)。然後，算出溶解度(質量%)=A/B×100。所算出的溶解度係依照以下之基準進行評價。 A：60質量%以上 B：50質量%以上且小於60質量% C：小於50質量%[Solubility] Put 288 g of distilled water in a 500 ml separable flask, and raise the temperature until the internal temperature reaches 85°C. After the temperature was raised, 12 g of ethylene-vinyl alcohol copolymer was added under stirring at 150 rpm. At a stage after 30 minutes passed after the addition, an aqueous ethylene-vinyl alcohol copolymer solution was collected. The collected aqueous solution was filtered with No. 5A filter paper, and the filtrate was dried at 125°C for 3 hours, and the mass A (g) of the ethylene-vinyl alcohol copolymer dissolved in the aqueous solution was determined. In addition, 12 g of sample ethylene-vinyl alcohol copolymer particles were dried at 125°C for 3 hours, and the non-volatile content B (g) was determined. Then, the solubility (mass %)=A/B×100 is calculated. The calculated solubility is evaluated according to the following criteria. A: 60% by mass or more B: 50% by mass or more and less than 60% by mass C: Less than 50% by mass

[塗覆液之羧酸的鹼金屬鹽含量之測定] 塗覆液之羧酸的鹼金屬鹽含量(鹼金屬的質量換算)係在白金坩堝內使乾固的塗覆液灰化後，使用Jarrell-Ash公司製ICP發光分析裝置「IRIS AP」，藉由測定所得之灰分中的鹼金屬量而求出。[Determination of alkali metal salt content of carboxylic acid in coating liquid] The alkali metal salt content of the carboxylic acid of the coating liquid (calculated by the mass of alkali metal) is the result of ashing the dry coating liquid in a platinum crucible, and then using the ICP emission analyzer "IRIS AP" manufactured by Jarrell-Ash. It is determined by measuring the amount of alkali metal in the ash content.

[塗覆紙之吸水性] 作為塗覆紙的耐水性之指標，依據JIS P 8140(1998年)，以柯布(Cobb)法，使用吸水度試驗器(商品名：Gurley Cobb Size Tester，熊谷理機工業公司製)測定吸水度。[Water Absorption of Coated Paper] As an indicator of the water resistance of the coated paper, the water absorption was measured by the Cobb method using a water absorption tester (trade name: Gurley Cobb Size Tester, manufactured by Kumagai Riki Co., Ltd.) in accordance with JIS P 8140 (1998) degree.

[塗覆紙之透氣度測定] 依據JIS P8117，使用王研式滑度透氣度試驗器，測定樣品之透氣度。 [塗覆紙之甲苯阻隔性評價][Determination of air permeability of coated paper] According to JIS P8117, use Wangyan-type slip air permeability tester to measure the air permeability of the sample. [Evaluation of toluene barrier properties of coated paper]

於樣品之塗覆面上塗布(5×5cm)經著色成紅色的甲苯，乾燥後，依照以下之基準判定往背面的透印(小的紅色斑點之發生或塗覆面全面之著色)程度。 A：在背面不發生斑點。 B：發生斑點，但著色面積為甲苯塗覆面之20%以下。 C：著色面積係比塗覆面的20%多且小於80%。 D：著色面積係塗覆面的80%以上。Coat (5×5cm) colored red toluene on the coated surface of the sample. After drying, determine the degree of print-through (the occurrence of small red spots or the coloration of the entire coated surface) on the back according to the following criteria. A: Spots do not occur on the back side. B: Spots occur, but the colored area is 20% or less of the toluene-coated surface. C: The colored area is more than 20% and less than 80% of the coated surface. D: The colored area is 80% or more of the coated surface.

[製造例1] (聚合步驟) 使用具備迴流冷卻器、原料供給管線、反應液取出管線、溫度計、氮氣導入口、乙烯導入口及攪拌翼之連續聚合槽。對於連續聚合槽，使用定量泵，連續地供給乙酸乙烯酯671L/hr、甲醇147L/hr、2,2’-偶氮雙(4-甲氧基-2,4-二甲基戊腈)的1%甲醇溶液2.6L/hr。以槽內乙烯壓力成為0.23MPa之方式調整。以聚合槽內的液面成為固定之方式，從連續聚合槽連續地取出聚合液。以連續聚合槽出口的聚合率成為30%之方式調整。連續聚合槽的滯留時間為5小時。連續聚合槽出口的溫度為60℃。從連續聚合槽回收聚合液，於所回收的液中導入甲醇蒸氣而去除未反應的乙酸乙烯酯單體，得到乙烯-乙烯酯共聚物(PVAc)之甲醇溶液(濃度32質量%)。[Manufacturing Example 1] (Polymerization step) Use a continuous polymerization tank equipped with a reflux cooler, a raw material supply line, a reaction liquid take-out line, a thermometer, a nitrogen inlet, an ethylene inlet, and a stirring blade. For the continuous polymerization tank, a quantitative pump was used to continuously supply 671L/hr of vinyl acetate, 147L/hr of methanol, and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). 1% methanol solution 2.6L/hr. Adjust so that the ethylene pressure in the tank becomes 0.23MPa. The polymerization solution was continuously taken out from the continuous polymerization tank so that the liquid level in the polymerization tank became fixed. Adjust so that the polymerization rate at the outlet of the continuous polymerization tank becomes 30%. The residence time in the continuous polymerization tank was 5 hours. The temperature at the outlet of the continuous polymerization tank was 60°C. The polymerization liquid was recovered from the continuous polymerization tank, and methanol vapor was introduced into the recovered liquid to remove unreacted vinyl acetate monomer, thereby obtaining a methanol solution of ethylene-vinyl ester copolymer (PVAc) (concentration 32% by mass).

(皂化步驟) 於前述聚合步驟所得之乙烯-乙烯酯共聚物的甲醇溶液(濃度32質量%)中，以相對於前述乙烯-乙烯酯共聚物中的乙酸乙烯酯單元而言氫氧化鈉之莫耳比成為0.01之方式，添加皂化觸媒之氫氧化鈉的甲醇溶液(濃度4質量%)。以靜態混合器混合乙烯-乙烯酯共聚物溶液及皂化觸媒溶液而得到混合物。將所得之混合物的糊載置於帶上，在40℃保持18分鐘而進行皂化反應。藉此，得到包含乙烯-乙烯醇共聚物與溶劑之固體塊。聚合條件及皂化條件係彙總於表1中。(Saponification step) In the methanol solution (concentration 32% by mass) of the ethylene-vinyl ester copolymer obtained in the aforementioned polymerization step, the molar ratio of sodium hydroxide to the vinyl acetate unit in the aforementioned ethylene-vinyl ester copolymer becomes 0.01 The method is to add a methanol solution of sodium hydroxide (concentration 4% by mass) as a saponification catalyst. The ethylene-vinyl ester copolymer solution and the saponification catalyst solution were mixed with a static mixer to obtain a mixture. The paste of the obtained mixture was placed on a belt and kept at 40°C for 18 minutes to proceed with the saponification reaction. Thereby, a solid block containing ethylene-vinyl alcohol copolymer and solvent is obtained. The polymerization conditions and saponification conditions are summarized in Table 1.

(粉碎步驟) 將在前述皂化步驟所得之固體塊以一軸剪切破碎機進行粉碎，得到濕粒子。於該破碎機中安裝洛氏硬度為45的破碎刀，破碎刀之旋轉數為250rpm。(Crushing step) The solid block obtained in the foregoing saponification step is pulverized with a shaft shear crusher to obtain wet particles. A crushing knife with Rockwell hardness of 45 is installed in the crusher, and the number of rotation of the crushing knife is 250 rpm.

(脫液步驟) 以螺旋排出型離心脫液機，將在前述粉碎步驟所得之濕粒子予以脫液，得到：通過孔徑5.6mm的篩之粒子的比例為94質量%，通過孔徑1.0mm的篩之粒子的比例為1.6質量%，溶劑之含有率為58質量%之脫液粒子。粉碎條件及脫液條件係彙總於表2中。(Deliquoring step) The wet particles obtained in the aforementioned pulverization step were deliquored by a screw-discharge centrifugal deliquoring machine, and the ratio of particles passing through the sieve of 5.6 mm diameter was 94% by mass, and the proportion of particles passing through the sieve of 1.0 mm diameter was 1.6% by mass, and the solvent content is 58% by mass. The pulverization conditions and deliquoring conditions are summarized in Table 2.

(乾燥步驟) 將在前述脫液步驟所得之脫液粒子600kg/hr(固體成分)連續地供給乾燥機，該乾燥機係以粒子溫度成為100℃之方式控制乾燥機內的溫度。乾燥機內的粒子之平均滯留時間為4小時。(Drying step) The 600 kg/hr (solid content) of the deliquored particles obtained in the aforementioned deliquoring step was continuously supplied to the dryer, and the temperature in the dryer was controlled so that the particle temperature became 100°C. The average residence time of the particles in the dryer is 4 hours.

(追加粉碎步驟) 以鎚磨機來追加粉碎在前述乾燥步驟所得之乾燥粒子，使其通過孔徑1.4mm的過濾器，得到乙烯-乙烯醇共聚物1。共聚物1中的乙烯單元之含有率為2莫耳%，黏度平均聚合度為1700，皂化度為93.0莫耳%。又，相對於100質量份的共聚物1，羧酸的鹼金屬鹽(乙酸鈉)之含量係以鹼金屬的質量換算(鈉換算)為0.33質量份。共聚物1的Cw(30℃)為9.7%，Cw(70℃)為2.1%，式(I)之值為6.9。又，於共聚物1全體之中，通過孔徑2.5mm的過濾器之比例為99質量%，通過孔徑1.0mm的過濾器之比例為94質量%，通過孔徑0.15mm的過濾器之比例為5質量%。依照上述方法評價共聚物1的粉塊性及溶解性，表3中顯示結果。(Add crush step) The dried particles obtained in the aforementioned drying step were additionally pulverized with a hammer mill and passed through a filter with a pore size of 1.4 mm to obtain an ethylene-vinyl alcohol copolymer 1. The content of the ethylene unit in the copolymer 1 was 2 mol%, the viscosity average polymerization degree was 1700, and the saponification degree was 93.0 mol%. In addition, the content of the alkali metal salt of carboxylic acid (sodium acetate) relative to 100 parts by mass of the copolymer 1 was 0.33 parts by mass in terms of the mass of alkali metal (sodium conversion). The Cw (30°C) of the copolymer 1 was 9.7%, the Cw (70°C) was 2.1%, and the value of the formula (I) was 6.9. In addition, in the entire copolymer 1, the ratio of passing through a filter with a pore size of 2.5 mm is 99% by mass, the ratio of passing through a filter with a pore size of 1.0 mm is 94% by mass, and the ratio of passing a filter with a pore size of 0.15 mm is 5% by mass. %. The lumps and solubility of copolymer 1 were evaluated according to the above-mentioned method, and the results are shown in Table 3.

[製造例2～11] 除了將聚合條件、皂化條件、粉碎條件及脫液條件變更為如表1及表2中所示以外，藉由與實施例1同樣之方法製造乙烯-乙烯醇共聚物(共聚物2～11)。表3中彙總顯示依照上述方法評價所得之共聚物的乙烯單元之含有率、聚合度、皂化度、羧酸的鹼金屬鹽之含量、粒度、30℃及70℃的水中結晶化度、式(I)之值的結果以及依照上述方法評價所得之共聚物的粉塊性及溶解性的結果。[Manufacturing Examples 2-11] Except that the polymerization conditions, saponification conditions, pulverization conditions, and deliquoring conditions were changed to those shown in Table 1 and Table 2, the ethylene-vinyl alcohol copolymer (copolymer 2-11) was produced by the same method as in Example 1. . Table 3 summarizes the content of ethylene unit, the degree of polymerization, the degree of saponification, the content of alkali metal salt of carboxylic acid, the particle size, the degree of crystallinity in water at 30°C and 70°C, the formula ( The result of the value of I) and the result of evaluating the blockability and solubility of the obtained copolymer according to the above method.

[表1] 聚合條件 皂化條件 乙烯 (MPa) 乙酸乙烯酯 (L/hr) 甲醇 (L/hr) 起始劑 (L/hr) 聚合率 (%) PVAc濃度 (質量%) NaOH (莫耳比) 製造例1 0.23 671 147 2.6 30 32 0.010 製造例2 0.1 618 2 168.2 78 45 0.008 製造例3 0.26 741 64 1.7 26 25 0.020 製造例4 0.47 726 113 2.2 28 30 0.012 製造例5 0.61 631 160 7.6 43 40 0.020 製造例6 0.69 626 170 75.8 70 45 0.015 製造例7 0.47 726 113 2.2 28 30 0.012 製造例8 0.23 671 147 2.6 30 32 0.010 製造例9 0.26 741 64 1.7 26 25 0.020 製造例10 0.23 671 147 2.6 30 32 0.010 製造例11 0.1 618 2 168.2 78 45 0.002 [Table 1] Polymerization conditions Saponification conditions Ethylene (MPa) Vinyl acetate (L/hr) Methanol (L/hr) Initiator (L/hr) Polymerization rate (%) PVAc concentration (mass%) NaOH (Morby) Manufacturing example 1 0.23 671 147 2.6 30 32 0.010 Manufacturing example 2 0.1 618 2 168.2 78 45 0.008 Manufacturing example 3 0.26 741 64 1.7 26 25 0.020 Manufacturing example 4 0.47 726 113 2.2 28 30 0.012 Manufacturing example 5 0.61 631 160 7.6 43 40 0.020 Manufacturing example 6 0.69 626 170 75.8 70 45 0.015 Manufacturing example 7 0.47 726 113 2.2 28 30 0.012 Manufacturing example 8 0.23 671 147 2.6 30 32 0.010 Manufacturing example 9 0.26 741 64 1.7 26 25 0.020 Manufacturing example 10 0.23 671 147 2.6 30 32 0.010 Manufacturing example 11 0.1 618 2 168.2 78 45 0.002

[表2] 粉碎條件 脫液條件 脫液粒子 旋轉數 (rpm) 洛氏 硬度 脫液機之種類 通過孔徑 5.6mm (質量%) 通過孔徑 1.0mm (質量%) 含液率 (質量%) 製造例1 250 45 螺旋排出型離心脫液機 94 1.6 58 製造例2 200 40 壓出板型離心脫液機 85 1.1 60 製造例3 400 50 螺旋排出型離心脫液機 85 0.1 50 製造例4 450 55 螺旋排出型離心脫液機 89 0.6 47 製造例5 500 55 螺旋排出型離心脫液機 87 0.5 44 製造例6 450 60 螺旋排出型離心脫液機 98 1.8 50 製造例7 550 60 螺旋排出型離心脫液機 99 1.9 43 製造例8 600 35 螺旋排出型離心脫液機 77 0.1 60 製造例9 450 60 壓榨脫液機 100 20 40 製造例10 600 35 壓榨脫液機 76 2.3 62 製造例11 600 35 壓榨脫液機 74 3.9 61 [Table 2] Crushing conditions Deliquoring conditions Deliquid particles Rotation number (rpm) Rockwell hardness Types of deliquor Through hole diameter 5.6mm (mass%) Pass aperture 1.0mm (mass%) Liquid content (mass%) Manufacturing example 1 250 45 Screw discharge type centrifugal deliquor 94 1.6 58 Manufacturing example 2 200 40 Extrusion plate type centrifugal deliquor 85 1.1 60 Manufacturing example 3 400 50 Screw discharge type centrifugal deliquor 85 0.1 50 Manufacturing example 4 450 55 Screw discharge type centrifugal deliquor 89 0.6 47 Manufacturing example 5 500 55 Screw discharge type centrifugal deliquor 87 0.5 44 Manufacturing example 6 450 60 Screw discharge type centrifugal deliquor 98 1.8 50 Manufacturing example 7 550 60 Screw discharge type centrifugal deliquor 99 1.9 43 Manufacturing example 8 600 35 Screw discharge type centrifugal deliquor 77 0.1 60 Manufacturing example 9 450 60 Press deliquor 100 20 40 Manufacturing example 10 600 35 Press deliquor 76 2.3 62 Manufacturing example 11 600 35 Press deliquor 74 3.9 61

[表3] 乙烯-乙烯醇共聚物粒子 評價 共聚物 乙烯單元之 含有率 (莫耳%) 聚合度 皂化度 (莫耳%) 羧酸的 金屬鈉鹽 (質量份) 通過 孔徑 2.5mm (質量%) 通過 孔徑 1.0mm (質量%) 通過 孔徑 0.15mm (質量%) Cw(30℃) (%) Cw(70℃) (%) 式(I)之值 粉塊性 溶解性 製造例1 共聚物1 2 1700 93.0 0.33 99 94 5 9.7 2.1 6.9 A A 製造例2 共聚物2 2 500 88.0 0.27 99 87 15 6.8 1.4 5.0 B A 製造例3 共聚物3 2 2300 99.3 0.80 80 4 0.1 49.6 15 17.4 A B 製造例4 共聚物4 4 1700 98.5 0.46 99 95 4 48.2 11.7 18.9 A A 製造例5 共聚物5 6 1000 99.2 0.82 99 93 7 51.4 16.8 16.8 A B 製造例6 共聚物6 10 400 98.0 0.58 99 93 12 69.1 26.7 13.1 A A 製造例7 共聚物7 4 1700 98.5 0.45 99 97 15 53.1 8.3 21.0 A B 製造例8 共聚物8 2 1700 93.0 0.36 99 96 7 4.9 1.3 3.4 C C 製造例9 共聚物9 2 2300 99.3 0.77 99 95 11 56 5.4 22.3 A C 製造例10 共聚物10 2 1700 93.0 0.38 99 94 7 4.6 1.6 2.9 C C 製造例11 共聚物11 2 500 80.0 0.08 99 96 21 3.9 1.1 2.7 C C [table 3] Ethylene-vinyl alcohol copolymer particles Evaluation Copolymer Ethylene unit content rate (mol%) Degree of polymerization Saponification degree (mol%) Metal sodium salt of carboxylic acid (parts by mass) Pass hole 2.5mm (mass%) Pass aperture 1.0mm (mass%) Pass aperture 0.15mm (mass%) Cw(30℃) (%) Cw(70℃) (%) Value of formula (I) Lumpy Solubility Manufacturing example 1 Copolymer 1 2 1700 93.0 0.33 99 94 5 9.7 2.1 6.9 A A Manufacturing example 2 Copolymer 2 2 500 88.0 0.27 99 87 15 6.8 1.4 5.0 B A Manufacturing example 3 Copolymer 3 2 2300 99.3 0.80 80 4 0.1 49.6 15 17.4 A B Manufacturing example 4 Copolymer 4 4 1700 98.5 0.46 99 95 4 48.2 11.7 18.9 A A Manufacturing example 5 Copolymer 5 6 1000 99.2 0.82 99 93 7 51.4 16.8 16.8 A B Manufacturing example 6 Copolymer 6 10 400 98.0 0.58 99 93 12 69.1 26.7 13.1 A A Manufacturing example 7 Copolymer 7 4 1700 98.5 0.45 99 97 15 53.1 8.3 21.0 A B Manufacturing example 8 Copolymer 8 2 1700 93.0 0.36 99 96 7 4.9 1.3 3.4 C C Manufacturing example 9 Copolymer 9 2 2300 99.3 0.77 99 95 11 56 5.4 22.3 A C Manufacturing example 10 Copolymer 10 2 1700 93.0 0.38 99 94 7 4.6 1.6 2.9 C C Manufacturing example 11 Copolymer 11 2 500 80.0 0.08 99 96 twenty one 3.9 1.1 2.7 C C

[實施例1] (塗覆紙之製作) 將共聚物1添加至經加溫到85℃的離子交換水，攪拌45分鐘而得到固體成分濃度為7質量%之溶液。相對於100質量份的共聚物1，該溶液中之羧酸的鹼金屬鹽(B)為0.33質量份。將其當作塗覆液，使用試驗用西姆施膠機(熊谷理機工業製)，以300m/分鐘之速度塗布於基重70g/m2 、透氣度20秒的PPC(普通紙複印機，plain paper copier)用紙上。以100℃的熱風乾燥機乾燥經塗布的紙5分鐘。所得之塗覆紙的塗覆量係以固體成分換算調整至0.5g/m2 。將所得之塗覆紙在20℃、65%RH下調濕72小時後，評價塗覆紙之物性。表4中顯示結果。[Example 1] (Production of coated paper) Copolymer 1 was added to ion-exchange water heated to 85°C, and stirred for 45 minutes to obtain a solution with a solid content of 7 mass%. The alkali metal salt of carboxylic acid (B) in the solution was 0.33 parts by mass relative to 100 parts by mass of copolymer 1. Using this as a coating liquid, using a test sim sizing machine (manufactured by Kumagai Riki Kogyo), it was applied to a PPC (plain paper copier, with a basis weight of 70 g/m 2 and an air permeability of 20 seconds) at a speed of 300 m/min. plain paper copier) on paper. The coated paper was dried with a hot air dryer at 100°C for 5 minutes. The coating amount of the obtained coated paper was adjusted to 0.5 g/m 2 in terms of solid content. After the obtained coated paper was humidified at 20°C and 65% RH for 72 hours, the physical properties of the coated paper were evaluated. The results are shown in Table 4.

[實施例2～7、比較例1～3、5] 除了代替實施例1之共聚物1，使用表4中所示的共聚物2～11以外，與實施例1同樣地製作塗覆紙。評價該塗覆紙的物性，表4中顯示結果。[Examples 2-7, Comparative Examples 1-3, 5] Except having used the copolymers 2-11 shown in Table 4 instead of the copolymer 1 of Example 1, it carried out similarly to Example 1, and produced the coated paper. The physical properties of the coated paper were evaluated, and the results are shown in Table 4.

[比較例4] 對於100質量份的共聚物3，混合1質量份的乙酸鈉，將所得之粉體添加至經加溫到85℃的離子交換水，攪拌45分鐘而得到固體成分濃度為7質量%之溶液。相對於100份的共聚物1，該溶液中之羧酸的鹼金屬鹽(B)為1.8質量份。將其當作塗覆液，使用試驗用西姆施膠機(熊谷理機工業製)，以300m/分鐘之速度塗布於基重70g/m2 、透氣度20秒的PPC(普通紙複印機)用紙上。以100℃的熱風乾燥機乾燥經塗布的紙5分鐘。所得之塗覆紙的塗覆量係以固體成分換算調整至0.5g/m2 。將所得之塗覆紙在20℃、65%RH下調濕72小時後，評價塗覆紙之物性。表4中顯示結果。[Comparative Example 4] For 100 parts by mass of copolymer 3, 1 part by mass of sodium acetate was mixed, and the resulting powder was added to ion-exchange water heated to 85°C, and stirred for 45 minutes to obtain a solid content concentration of 7 Mass% solution. The alkali metal salt of carboxylic acid (B) in this solution is 1.8 parts by mass relative to 100 parts of copolymer 1. Use it as a coating liquid and use a test Sim sizing machine (manufactured by Kumagai Riki Kogyo) to apply it to a PPC (plain paper copier) with a basis weight of 70 g/m 2 and an air permeability of 20 seconds at a speed of 300 m/min. Use paper. The coated paper was dried with a hot air dryer at 100°C for 5 minutes. The coating amount of the obtained coated paper was adjusted to 0.5 g/m 2 in terms of solid content. After the obtained coated paper was humidified at 20°C and 65% RH for 72 hours, the physical properties of the coated paper were evaluated. The results are shown in Table 4.

[表4] 塗覆液 塗覆紙評價 共聚物(A) 羧酸的鹼金屬鹽(B) 吸水度 透氣度 甲苯阻隔性 (質量份) (g/m2 ) (秒) 實施例1 共聚物1 0.33 43 54000 A 實施例2 共聚物2 0.27 70 26000 B 實施例3 共聚物3 0.8 27 64000 A 實施例4 共聚物4 0.46 22 45000 A 實施例5 共聚物5 0.82 22 43000 A 實施例6 共聚物6 0.58 30 33000 A 實施例7 共聚物7 0.45 44 30000 A 比較例1 共聚物8 0.36 55 8800 D 比較例2 共聚物9 0.77 49 11000 C 比較例3 共聚物10 0.38 57 8400 D 比較例4 共聚物3 1.8 50 14000 C 比較例5 共聚物11 0.08 75 7000 D [Table 4] Coating liquid Coated paper evaluation Copolymer (A) Alkali metal salt of carboxylic acid (B) Water absorption Air permeability Toluene barrier (Parts by mass) (g/m 2 ) (second) Example 1 Copolymer 1 0.33 43 54000 A Example 2 Copolymer 2 0.27 70 26000 B Example 3 Copolymer 3 0.8 27 64000 A Example 4 Copolymer 4 0.46 twenty two 45,000 A Example 5 Copolymer 5 0.82 twenty two 43000 A Example 6 Copolymer 6 0.58 30 33000 A Example 7 Copolymer 7 0.45 44 30000 A Comparative example 1 Copolymer 8 0.36 55 8800 D Comparative example 2 Copolymer 9 0.77 49 11000 C Comparative example 3 Copolymer 10 0.38 57 8400 D Comparative example 4 Copolymer 3 1.8 50 14000 C Comparative example 5 Copolymer 11 0.08 75 7000 D

如表4所示，塗布實施例1～7所得之塗覆液而得的塗覆紙，係透氣度之值大，阻隔性優異。而且，實際上甲苯阻隔性亦優異。因此，可知使用本發明之塗覆液而形成有填隙層之塗覆紙，係在該填隙層之上塗布剝離層而形成時，聚矽氧樹脂之表面良率高，具有能製造剝離紙之充分性能。As shown in Table 4, the coated paper obtained by applying the coating liquids obtained in Examples 1 to 7 has a large air permeability and excellent barrier properties. Moreover, in fact, toluene barrier properties are also excellent. Therefore, it can be seen that the coated paper with a gap-filling layer formed by using the coating liquid of the present invention is formed by coating a release layer on the gap-filling layer. Full performance of paper.

無。no.

無。no.

無。no.

Claims (7)

一種紙用塗覆液，其係包含乙烯-乙烯醇共聚物(A)及羧酸的鹼金屬鹽(B)之紙用塗覆液； 該乙烯-乙烯醇共聚物(A)的乙烯單元之含有率為1莫耳%以上且小於20莫耳%， 以脈衝NMR求出之在30℃的水中結晶化度Cw(30℃)及在70℃的水中結晶化度Cw(70℃)滿足下述式(I)，且 相對於100質量份的該乙烯-乙烯醇共聚物(A)，以鹼金屬的質量換算含有0.001～1質量份的該羧酸的鹼金屬鹽(B)；
Figure 03_image001
。A paper coating liquid comprising an ethylene-vinyl alcohol copolymer (A) and an alkali metal salt of a carboxylic acid (B); the ethylene unit of the ethylene-vinyl alcohol copolymer (A) The content rate is 1 mol% or more and less than 20 mol%, the crystallinity degree Cw (30℃) in water at 30℃ and the crystallinity degree Cw (70℃) in water at 70℃ obtained by pulse NMR meet the requirements Formula (I), and relative to 100 parts by mass of the ethylene-vinyl alcohol copolymer (A), the alkali metal salt (B) of the carboxylic acid is contained in an amount of 0.001 to 1 part by mass based on the mass of the alkali metal;
Figure 03_image001
. 如請求項1之紙用塗覆液，其中該乙烯-乙烯醇共聚物(A)之皂化度為90～98.5莫耳%。The coating liquid for paper of claim 1, wherein the saponification degree of the ethylene-vinyl alcohol copolymer (A) is 90-98.5 mol%. 如請求項1或2之紙用塗覆液，其中該乙烯-乙烯醇共聚物(A)之黏度平均聚合度為900～2400。The coating liquid for paper of claim 1 or 2, wherein the ethylene-vinyl alcohol copolymer (A) has an average polymerization degree of viscosity of 900-2400. 一種塗覆紙，其係將如請求項1至3中任一項之塗覆液塗布於紙之表面而成。A coated paper, which is formed by coating the coating liquid of any one of claims 1 to 3 on the surface of the paper. 如請求項4之塗覆紙，其係剝離紙用原紙。Such as the coated paper of claim 4, which is a base paper for release paper. 一種剝離紙，其係在將如請求項1～3之塗覆液塗布於紙上而形成的填隙層之上，形成剝離層而成。A release paper which is formed by forming a release layer on a gap-filling layer formed by coating the coating liquid of Claims 1 to 3 on paper. 如請求項6之剝離紙，其中剝離層包含聚矽氧樹脂。Such as the release paper of claim 6, wherein the release layer contains silicone resin.
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