阅读说明：本技术 含有低度官能化的部分皂化聚乙酸乙烯酯的可辐照固化的混合物 (The mixture of radiation-curable containing low functionalized partly-hydrolysed polyvinyl acetate ) 是由 C·皮奇 A·贝克尔 U·克劳斯 T·特尔瑟 于 2018-01-26 设计创作，主要内容包括：本发明涉及用于产生凸纹结构的可辐照固化的混合物,其包含：a)作为组分A的至少一种官能化的部分水解的聚乙酸乙烯酯,其包含(i)乙烯醇单元、(ii)乙酸乙烯酯单元和(iii)丙烯酸乙烯酯单元,其中丙烯酸乙烯酯单元可以是被取代的,具有通式(I)结构,其中R是氢,或直链或支化的具有1-12个碳原子的脂族或杂脂族基团,或具有3-12个碳原子的脂环族、杂环或芳族基团,b)作为组分B的至少一种引发剂,c)作为组分C的至少一种与组分A不同的烯属不饱和化合物,d)作为组分D的一种或多种助剂,其特征在于在官能化的部分水解的聚乙酸乙烯酯a)中,丙烯酸乙烯酯单元(iii)的量是基于全部单元(i)、(ii)和(iii)计的0.1摩尔％至<3摩尔％,并且组分D包含能形成氢键的添加剂,组分D的量是基于组分A至D总和计的0.001-30重量％。<Image he="352" wi="535" file="DDA0002214211670000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to the mixtures of the radiation-curable for generating raised lines structure, it includes: a) polyvinyl acetate as at least one functionalized partial hydrolysis of component A, it includes (i) vinyl alcohol units, (ii) vinyl acetate unit and (iii) vinyl ester units, wherein vinyl ester units can be substituted, with logical formula (I) structure, wherein R is hydrogen, or straight chain or the aliphatic series or Heteroaliphatic groups with 1-12 carbon atom of branching, or it is alicyclic with 3-12 carbon atom, heterocycle or aromatic group, b) as at least one initiator of component B, c) as at least one olefinic unsaturated compound different from component A of component C, d) as one or more auxiliary agents of component D, it is characterized in that in the poly- second of functionalized partial hydrolysis In vinyl acetate a), the amount of vinyl ester units (iii) is 0.1 mole of % to < 3 moles of % based on whole units (i), (ii) and (iii), and component D includes the additive that can form hydrogen bond, and the amount of component D is the 0.001-30 weight % based on component A to D summation meter.)

1. it is a kind of for generating the mixture of the radiation-curable of raised lines structure, it includes:

A) polyvinyl acetate as at least one functionalized partial hydrolysis of component A, it includes (i) vinyl alcohol units, (ii) vinyl acetate unit and (iii) vinyl ester units, wherein vinyl ester units can be substituted, With following general formula structure:

Wherein R is the hydrogen perhaps aliphatic series with 1-12 carbon atom of straight chain or branching or Heteroaliphatic groups or with 3-12 The alicyclic of a carbon atom, heterocycle or aromatic group,

B) as at least one initiator of component B,

C) as at least one olefinic unsaturated compound different from component A of component C,

D) as one or more auxiliary agents of component D,

It is characterized in that in the polyvinyl acetate a) of functionalized partial hydrolysis, the amount of vinyl ester units (iii) It is 0.1 mole of % to < 3 moles of % based on whole units (i), (ii) and (iii), and component D includes that can form hydrogen bond Additive, the amount of component D is the 0.001-30 weight % based on component A to D summation meter.

2. the mixture of radiation-curable according to claim 1, it is characterised in that in component A, vinyl alcohol units (i) Amount be 65-99 moles of % based on whole units (i), (ii) and (iii).

3. the mixture of radiation-curable according to claim 1 or 2, it is characterised in that in component A, vinyl acetate The amount of unit (ii) is the 5-35 moles of % based on whole units (i), (ii) and (iii).

4. the mixture of radiation-curable according to any one of claim 1-3, it is characterised in that the amount of component A It is the 5-75 weight % based on component A to D summation meter.

5. the mixture of radiation-curable described in any one of -4 according to claim 1, it is characterised in that the amount of component B It is the 0.1-20 weight % based on component A to D summation meter.

6. the mixture of radiation-curable according to any one of claims 1-5, it is characterised in that the olefinic of component C is not Saturated compounds includes at least one vinyl ether group and/or acrylate group and/or methacrylate group.

7. the mixture of radiation-curable according to claim 1 to 6, it is characterised in that the amount of component C It is the 0.5-50 weight % based on component A to D summation meter.

8. the mixture of radiation-curable described in any one of -7 according to claim 1, it is characterised in that additive is to be selected from Plasticizer, solvent, other adhesives, colorant, stabilizer, chain-transferring agent, UV absorbent, dispersing aid, non-free radical crosslinking The crosslinking agent of type, viscosity improver, and receive the additive of hydrogen bond.

9. the mixture of radiation-curable according to claim 1 to 8, it is characterised in that the amount of component D It is the 1-50 weight % based on component A to D summation meter.

10. the mixture of radiation-curable according to claim 1 to 9, it is characterised in that hydrogen bond can be formed Additive is selected from polyvinyl alcohol, polyvinyl acetate, polyethyleneimine, polyurethane, polyethylene glycol and polyvinyl alcohol/poly- second Glycol graft copolymer.

11. a kind of sandwich type element of radiation-curable, according to claim 1 any one of -10 on carrier are included at least The burr forming layer of the mixture of the radiation-curable.

12. the sandwich type element of radiation-curable according to claim 11, wherein on burr forming layer or in burr shape Lower stratification includes at least one other layer selected from the following: protective layer, releasing layer, mask layer, barrier layer, for generating surface knot The layer and adhesive layer of structure or any desired a combination thereof.

13. a kind of have the more of raised lines structure from the production of the sandwich type element of radiation-curable according to claim 11 or 12 The method of layer elements, including irradiating burr forming layer via mask layer that is integration or can applying, and it is cambial to remove burr Uncured region.

14. a kind of have the more of raised lines structure from the production of the sandwich type element of radiation-curable according to claim 11 or 12 The method of layer elements, including irradiate burr forming layer and by relief engraving at the cambial cured region of burr.

Embodiment

Method:

The method for detecting degree of functionalization:

In the first step, it is purified for the sample of detection with elimination reaction residue, especially monomer.This passes through use 200g acetone is carried out via the sample of the Soxhlet extractron purification about 12g at 56 DEG C.Then at decompression (about 100mbar) It is 2 hours dry at 70 DEG C.10% solution (w%, normal propyl alcohol=50%) of the preparation purification sample in n-propanol/water, and record Actual solid content.This solution of 5g is weighed, and is added in 50mL container together with 2g potassium hydroxide (aq.2mol/L).By sample Product are placed 4 hours in cabinet drier and are adjusted at 93 DEG C.In order to neutralize, weighs and 3g hydrochloric acid (2mol/L) is added.Then, by sample Product vibrate 45 minutes at 450 rpm on 130 vibration of foundation device (IKA) of IKA.Lid is opened, weighs and 35g acetone and the last of the ten Heavenly stems is added Alcohol is as internal standard (1500g acetone/0.51g 1- decyl alcohol).On 130 vibration of foundation device (IKA) of IKA at 450 rpm by sample Mixing 1.5 hours.This solution is assigned in 2mL GC bottle with injecting fluid with 0.25 μm of syringe-driven filter.These are small Bottle be placed in Autosampler, and with outfit TriPlus 100LS gas-chromatography TRACE 1300GC (Thermo Fisher Scientific it) is analyzed with Chromeleon software (version 7.2.), the result is that as methacrylic acid (MAA) and acetic acid (acetic) it obtains, unit is mg/g.This using FFAP column (Chromatographie Service GmbH) at 220 DEG C and Carried out under 175kPa, the length is 50m, occupation rate 0.25mm, fid detector, and using hydrogen (6.0, come from Air Liquide) it is used as carrier gas.

It is assumed that the mole of the acrylic acid and acetic acid that optionally replace corresponds respectively to be present in the acrylic acid in polymer Assessment result on the basis of the mole of vinyl ester units and vinyl acetate unit, and assume vinyl alcohol units, acrylic acid The summation of vinyl ester units and/or the molar ratio of vinyl acetate unit is 100%.Methacrylate vinyl base is used as follows Ester illustrates as an example.The conversion of the numerical value of the methacrylic acid (mg/g) analyzed from GC and acetic acid (mg/g) is used for official Can fluidized polymer complete soln (unit is g), wherein quality m_MAAAnd m_{Acetic acid}Unit be g.It is following to calculate molal weight:

AndSo

Wherein

Thus functionalization is obtained, unit %:

Detect stress-strain:

The detection of stress-strain is (to be free of cover foil and carrier foils, they are in exposed, washing and dry sample Be stripped in advance) on carry out, use the version (that is, face outwardly is exposed, and not having structuring) of full depth.Corresponding Experiment in report exposure, rinse and drying condition.After the drying, these versions are stored overnight at room temperature, and used Zwick sample pattern 5A (come from Zwick Roell AG) punching press obtains that measurement length is 20mm and measurement width 4mm is four A sample.Herein it should be ensured that there is no damage (crackle etc.) and/or foreign body (such as air bubble, particles in the sample Deng).Using 72.5 instrument of Zwick Roell (coming from Zwick Roell AG) and test special-purpose software version V10.0 according to base It is detected in the method for DIN 53504, wherein prestretching force is 0.01MPa, and strain rate at room temperature is 100mm/min.4 samples are detected in each case, and reporting unit is the elongation at break ε R and unit N/mm of %²Bend Take stress σ_maxArithmetic mean of instantaneous value.

The viscosity of the polyvinyl acetate of detection part hydrolysis:

Viscosity is detected in 4% aqueous solution in 20 DEG C according to DIN 53 015 using falling ball viscometer.

Detect the viscosity of radiation sensitivity mixture:

Using 550 rotational viscometer of HAAKE Viscotester of outfit MV measuring cup according to DIN 53019 at 60 DEG C Lower detection viscosity, wherein rotation speed is 64 revs/min.

Detect the time for exposure:

In order to detect the time for exposure, protective foil is removed from version, is then usedCombi CW 35x 50 (Flint Group) exposes different time, this apparatus preparation TL 09 is managed, and carry out via experiment negative film (Reprofilm,1C Testform nyloprint is conventional, 2540dpi, 45° angle).It is being washed off with waterCombi After CW 35x 50 (Flint Group), it is 65 DEG C of dryings after ten minutes, measures the time for exposure, wherein in the feelings of not error 2% halftoning mesh sheet (halftone screen) (59L/cm) is reappeared under condition.

DetectionIt rinsesTime:

In order to detect washing time, unexposed version water existsCombi CW 35x50(Flint Group it is washed in) until photosensitive layer is completely removed.Time needed for reaching this purpose is reported as washing time, and unit is point Clock.

It is dry:

Washed version existsIn Combi CW 35x 50 (Flint Group) drier at 65 DEG C It is 10 minutes dry.

Detection curling:

In order to detect curling, protective layer is removed from the version having a size of 20x 20cm, then with outfit 09 pipe of TLCombi CW 35x 50 (Flint Group) exposes the corresponding time to form 2% halftoning mesh sheet (59L/cm), unit are minute (be free of negative film), and are developed (for specific version, be rinsed with water accordingly time) and dry. Then these versions are stored 3 days at room temperature.During this period, the direction that 4 corners of these editions face away from substrate scrolls up It rises.At two angles with peak, the distance between this angle and substrate are detected, unit is millimeter, and calculates and report this The arithmetic mean of instantaneous value of two detected values.

Evaluate the print result for high light portion:

In addition, UVONOVA (Flint Group) carries out printing experiment using UV letterpress inks.In this experiment, Galley is stretched on printing roller and is printed on conventional letter press device (printing machine: Nilpeter-F 2400).Print Brush substrate is " High Gloss White Premium " paper, with single side coating, comes from Avery Dennison.Printing speed Degree is 25m/min.The size of halftoning mesh sheet be 59 lines/centimetre.Detection is the tone value added (1% by feature track To 10% half-tone regions) it is constituted relative to ideal tone initial value (1:1 curve).The result of printing experiment is summarised in table 4-5 In 6.After printing, crackle of the observation galley in solid area.